CN108107688A

CN108107688A - Electrophtography photosensor

Info

Publication number: CN108107688A
Application number: CN201711159334.3A
Authority: CN
Inventors: 前田诚亮; 栗本和典; 仓持和裕
Original assignee: Konica Minolta Opto Inc
Current assignee: Konica Minolta Inc; Konica Minolta Opto Inc
Priority date: 2016-11-24
Filing date: 2017-11-20
Publication date: 2018-06-01
Also published as: EP3327508B1; JP2018084688A; US20180143545A1; EP3327508A1; US10175591B2; JP6753280B2

Abstract

The present invention provides a kind of discharge deterioration when carrying roller strap electric system during inhibition roller strap electricity, excellent in abrasion resistance and the Electrophtography photosensor that can be imaged as good image.The present invention can be reached by Electrophtography photosensor, the Electrophtography photosensor is sequentially laminated with charge generation layer, charge transport layer in conductive support body, it is characterized in that, the composite construction particle that the layer for forming the most surface of above-mentioned Electrophtography photosensor is inorganic particulate containing core and coating is formed doped with the tin oxide of aluminium on above-mentioned inorganic particulate, the average grain diameter of the primary particle of above-mentioned composite construction particle is 50~200nm.

Description

Electrophtography photosensor

Technical field

The present invention relates to Electrophtography photosensor (following, to be also referred to as photoreceptor).

Background technology

As the charged method in the imaging process of electrofax, use the contact for using roller etc. charged method (with Under, it is also referred to as roller strap electric system).Roller strap electric system is compared with using the band of line etc. electrically (grid electrode electrified system), energy Enough carry out low energy under charged or uniform charged, be through frequently with band electrically.

In the past, when carrying roller strap electric system, ultraviolet curable resin and reactive electricity are made as patent document 1,2 Lotus agent delivery carries out reaction and cures to attempt to have both electrical characteristics and intensity.

When attempting to have both electrical characteristics and intensity, carry out largely further adding electroconductive particle in most surface layer The research of (electroconductive stuffing).In electric discharge in roller strap electricity, electroconductive stuffing becomes the earth point of electric discharge, can become because of electric discharge Caused deterioration position.Deterioration position during in order to reduce electric discharge, can be by adding that powder resistance value is low and grain size is big leads Conductive particles are come reduction discharge deterioration position while ensuring the volume of the electroconductive particle in most surface layer.By using grain size Big electroconductive particle (also referred to as big grain size electroconductive particle), can obtain wearability, but the spot diameter of sub-image is easily spread, difficult To obtain very thin image.

As the most surface layer for using big grain size electroconductive particle, there is the example enumerated in patent document 3, band is electrically Grid electrode mode, can improve wearability and Memorability, but not on sub-image clarity description.In addition, similarly Also by big grain size electroconductive particle for most surface layer in patent document 4, but not especially in regard to the record of sub-image.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2014-199391 publications

Patent document 2：Japanese Unexamined Patent Publication 2015-099354 publications

Patent document 3：Japanese Unexamined Patent Publication 6-295086 publications

Patent document 4：Japanese Unexamined Patent Publication 2014-186192 publications

The content of the invention

That is, there are the following problems in the technology recorded in Patent Documents 1 to 4：By being led in most surface layer using big grain size Conductive particles can obtain wearability, but the spot diameter of sub-image is easily spread, it is difficult to obtain very thin image.

Therefore, it is an object of the invention to provide it is a kind of can inhibit roller strap electricity when carrying roller strap electric system when electric discharge it is bad Change, excellent in abrasion resistance and the Electrophtography photosensor that good image can be imaged as.

In order to solve the above problems, further investigation has been repeated in the inventors of the present invention.Itself it turns out that, by form feel Contain the coating on inorganic particulate in the layer of the most surface of body of light has defined once grain doped with what the tin oxide of aluminium formed The composite construction particle in footpath, can reach above-mentioned purpose, complete the present invention.

That is, above-mentioned purpose of the invention can be reached by following composition.

(1) a kind of Electrophtography photosensor is sequentially laminated with charge generation layer, charge conveying in conductive support body Layer, which is characterized in that

The layer for forming the most surface of above-mentioned Electrophtography photosensor contains core for inorganic particulate and in above-mentioned inorganic particulate The composite construction particle that upper coating is formed doped with the tin oxide of aluminium,

The average grain diameter of the primary particle of above-mentioned composite construction particle is 50~200nm.

(2) Electrophtography photosensor according to above-mentioned (1), which is characterized in that above-mentioned inorganic particulate is BaSO₄、 SiO₂、Al₂O₃Any one of.

(3) Electrophtography photosensor according to above-mentioned (1) or (2), which is characterized in that be coated above-mentioned inorganic particulate Doped with aluminium tin oxide compared with the Al of 100 mass parts of tin oxide doping be 0.05~1 mass parts scope, it is above-mentioned multiple The volume resistivity for closing structured particles is 10¹~10⁸Ωcm。

(4) Electrophtography photosensor according to any one of above-mentioned (1)~(3), which is characterized in that above-mentioned composite junction Structure particle using compared with 100 mass parts of composite construction particle not being surface-treated as 0.5~10 mass parts in the range of Surface conditioning agent with polymerism reactive group be surface-treated,

Above-mentioned surface conditioning agent is the silane coupling agent containing acryloyl group or methylacryloyl.

(5) Electrophtography photosensor according to any one of above-mentioned (1)~(4), which is characterized in that above-mentioned composite junction Structure particle compared with 100 mass parts of composite construction particle as the fluororesin in the range of 1~10 mass parts to be coated.

(6) Electrophtography photosensor according to any one of above-mentioned (1)~(5), which is characterized in that form above-mentioned electricity The layer of the most surface of sub- electrophotographic photoconductor further contains resinoid bond,

The content of above-mentioned composite construction particle is 50~250 mass parts compared with above-mentioned 100 mass parts of resinoid bond Scope.

(7) Electrophtography photosensor according to recorded in above-mentioned (6), which is characterized in that above-mentioned resinoid bond is polymerization The polymerizing curable object of property compound.

(8) a kind of image forming apparatus, which is characterized in that have：

Electrophtography photosensor any one of above-mentioned (1)~(7),

For make the surface of above-mentioned Electrophtography photosensor charged charged mechanism,

Formed for the surface irradiation light to charged above-mentioned Electrophtography photosensor electrostatic latent image exposure mechanism,

Toner image is formed for supplying toner to the above-mentioned Electrophtography photosensor for being formed with electrostatic latent image Developing mechanism and

For the above-mentioned toner image on the surface of above-mentioned Electrophtography photosensor to be transferred to the transfer interpreter of recording medium Structure,

Above-mentioned charged mechanism is to be applied for the surface with above-mentioned Electrophtography photosensor close to (comprising the mode contacted) Add the charged mechanism (above-mentioned roller strap electric system) close to band electrically of electrified voltage.

According to the present invention it is possible to provide a kind of discharge deterioration of photoreceptor when inhibiting electric discharge, excellent in abrasion resistance and can be into Photoreceptor as being good image.

Description of the drawings

Fig. 1 is the explanation sectional view of an example of the composition for representing the image forming apparatus of the present invention.

Fig. 2 is to represent the example that the layer for forming the Electrophtography photosensor of the image forming apparatus of the present invention is formed Partial section view.

Fig. 3 is the explanation section of an example of the composition for representing the charged roller in image forming apparatus shown in FIG. 1 Figure.

Fig. 4 is contained in the layer of the most surface for the Electrophtography photosensor for representing the image forming apparatus of the composition present invention The explanation sectional view of one example of the composition of composite construction particle and its particle structure of manufacturing process.Fig. 4 (a) is to represent The explanation sectional view of one example of the inorganic particulate structure prepared in the manufacturing process of composite construction particle.Fig. 4 (b) is table Show an example of the structure for the composite construction particle that coating is formed doped with the tin oxide of aluminium on the inorganic particulate of Fig. 4 (a) Explanation sectional view.Fig. 4 (c) is to represent with surface conditioning agent be surface-treated by the composite construction particle of Fig. 4 (b) Composite construction particle structure an example explanation sectional view.Fig. 4 (d) is to represent Fig. 4 (c) to be surface-treated One example of the structure for the composite construction particle that the composite construction particle that agent is surface-treated is formed with fluororesin coating Explanation sectional view.

Symbol description

10 photoreceptors,

10a conductive support bodies,

10b interlayers,

10c charge generation layers,

10d charge transport layers,

10e most surface layers,

10f organic photosensitive layers,

11 charged rollers,

11a plugs,

11b elastic layers,

11c resistance key-courses,

11d superficial layers,

11e presses pressing spring,

12 exposure mechanisms,

13 developing mechanisms,

13a development sleeves,

14 transfer means,

15 cleaning rollers,

17 fixing mechanisms,

18 cleaning mechanisms,

18a cleaning baldes,

18b storage parts,

21 inorganic particulates (core),

23 mix Al tin oxide,

25 composite construction particles,

The composite construction particle that 25a is surface-treated,

25b has carried out the composite construction particle of surface treatment and fluororesin coating,

27 Surface Treated Films,

29 fluororesin films,

P transfer materials.

Specific embodiment

Hereinafter, the present invention is concretely demonstrated.

(image forming apparatus)

The image forming apparatus of one embodiment of the present invention is characterized in that having：

Electrophtography photosensor with composition as shown below,

Above-mentioned charged mechanism is to be applied for the surface with above-mentioned Electrophtography photosensor close to (comprising the form contacted) Add the charged mechanism (above-mentioned roller strap electric system) close to band electrically of electrified voltage.By with above-mentioned composition, inhibiting to put The discharge deterioration of photoreceptor when electric, excellent in abrasion resistance and can be imaged as good image aspect it is excellent.

The present invention image forming apparatus in, using make Electrophtography photosensor surface it is electronegative close to band electrically Charged mechanism (roller strap electric system).Image with this charged mechanism (roller strap electric system) close to band electrically forms dress Putting can be as the charged roller of the charged mechanism and the photoreceptor composition being placed in contact with or the structure closely set Into.

Fig. 1 is the explanation sectional view of an example of the composition for representing the image forming apparatus of the present invention.It is shown in FIG. 1 Image forming apparatus has：The photoreceptor 10 of drum type as electrostatic latent image carrying body；Possess by being same pole with toner Property corona discharge etc. the surface of the photoreceptor 10 is made equally electronegative charged roller 11 and to clean connecing for its cleaning roller 15 The nearly charged mechanism of band electrically；By on the surface of equally charged photoreceptor 10 polygon mirror etc. being utilized to be based on picture number According to the exposure mechanism 12 for carrying out image exposure and forming electrostatic latent image；Possess the development sleeve 13a of rotation and will remain in it On toner be transported to the surface of photoreceptor 10 and make above-mentioned electrostatic latent image developing and form the developing mechanism of toner image 13；The toner image is transferred to the transfer means 14 of transfer materials P as needed；Make the toner figure on transfer materials P As fixing fixing mechanism 17；And the cleaning mechanism with the cleaning balde 18a for removing the remaining toner on photoreceptor 10 18。

(Electrophtography photosensor)

The Electrophtography photosensor of an embodiment of the invention is sequentially laminated with charge production in conductive support body Generating layer, charge transport layer, which is characterized in that the layer for forming the most surface of above-mentioned Electrophtography photosensor contains core for inorganic grain Son and the composite construction particle that coating is formed doped with the tin oxide of aluminium on above-mentioned inorganic particulate, above-mentioned composite construction particle The average grain diameter of primary particle is 50~200nm.By being set to this composition, photoreceptor during a kind of inhibition electric discharge can be provided Discharge deterioration, excellent in abrasion resistance and the photoreceptor that good image can be imaged as.

In the present invention, a kind of, excellent in abrasion resistance strong to discharge deterioration can be provided, the photosensitive of good image quality can be imaged as Body.Why using the present invention Electrophtography photosensor can obtain this effect, for its expression mechanisms or the mechanism of action (machine System), although not yet clearly, being presumed as follows.

The photoreceptor of the present invention contains the inorganic particulate for being useful for assigning mechanical strength in its most surface layer, but in order to make its tool There is the patience to electric discharge, preferably comprise resinoid bond (preferably utilizing the polymerizing curable object of photopolymerization reaction) and for assigning The inorganic particulate of mechanical strength.Inorganic particulate needs undertake electrical characteristics simultaneously, and it is necessary to have electric conductivity.In order to be assigned to inorganic particulate Give electric conductivity, using by inorganic particulate as core and in a manner that tin oxide is coated the composite construction particle that the inorganic particulate forms Contain.

Think to assign electric conductivity as to above-mentioned inorganic particulate, it is preferred to use nucleocapsid.Since charge is maintained at It is whole including the particle in electroconductive particle, therefore positive charge can not eliminate negative electrical charge existing for inside electroconductive particle.Cause This, it is also preferred that negative electrical charge is present in electroconductive particle surface element in electroconductive particle.Therefore, it is good to become core portion insulating properties of trying one's best Composition good and that preferred electroconductive particle as electric conductivity is assigned to shell portion.

In addition, in order to maintain electrical characteristics in the most surface layer of the photoreceptor containing particle and reduce point of discharge, can be put into The big particle of grain size, reduces spark location.But in this case, number is reduced, therefore in order to maintain electrical characteristics, It needs to reduce the powder resistance of electroconductive particle and reduce the resistance as most surface layer.However, in the most table of such property Surface layer forms sub-image time point and easily spreads, can not form very thin image.

In order to solve the problem, it is necessary to adjust the volume resistivity of conductive surface of inorganic particles.For volume The adjustment of resistivity, tin oxide is useful as the material of coating inorganic particulate, as further adjustment coating inorganic particulate Tin oxide volume resistivity method, it is found that adulterated al is useful and adjustable in tin oxide.

In addition, as the method that resistance (volume resistivity) is adjusted with dopant, it can be by adding the valence mumber compared with tin Different members usually adjust.In addition, as dopant, antimony, tantalum etc. can be also enumerated, in antimony dopant, the most table that is formed sometimes Surface layer becomes lividity due to the influence of dopant, it is possible to can not form the coated film with the required transparency.In order to It controls to be suitable for the resistance value of photosensitive surface (most surface layer), it is necessary to the resistance of tin oxide be improved, for the height of tin oxide Resistance, it is known that the aluminium of trivalent is suitable.It is also known that although antimony is also excellent as dopant, due to being 5 valencys, having makes The tendency of tin oxide low resistance, the resistance adjustment in photoreceptor purposes become difficult.Furthermore, it is possible to it says from the environment caused by antimony Also do not recommend from the perspective of load, cost.It was found that the tune from the volume resistivity for embodying the electrical characteristics as photosensitive bulk properties From the perspective of whole easiness, aluminium that is cheap and being easily processed is useful.So, it is believed that pass through the most surface in photoreceptor Layer can be become to the indefatigable composite construction particle that discharges, be passed through with the inorganic particulate doped with the tin oxide of Al coating core Containing the particle, discharge deterioration during roller strap electricity, excellent in abrasion resistance are can inhibit, and good image can be imaged as.It is in addition, above-mentioned Expression mechanisms or the mechanism of action obtain by inference, the present invention and from above-mentioned expression mechanisms or any limit of the mechanism of action It is fixed.

Hereinafter, the composition of the Electrophtography photosensor of the present invention is illustrated.

As the Electrophtography photosensor that the layer with the present invention is formed, for example, as shown in Fig. 2, in conductive support body Interlayer 10b, charge generation layer 10c, charge transport layer 10d and most surface layer 10e are stacked gradually on 10a and forms photoreceptor 10.Photosensitive layer 10f essential to the composition of photoreceptor is formed by charge generation layer 10c and charge transport layer 10d.In most table In surface layer 10e, containing core for inorganic particulate and on above-mentioned inorganic particulate coating doped with aluminium tin oxide form it is compound Structured particles (average grain diameter of primary particle is 50~200nm).

(most surface layer)

The layer (also referred to as most surface layer) of the most surface of the Electrophtography photosensor of the composition present invention is inorganic containing core Particle and coating is formed doped with the tin oxide of aluminium (Al) on above-mentioned inorganic particulate composite construction particle (primary particle it is flat Equal grain size is 50~200nm).Preferably, above-mentioned most surface layer further contains resinoid bond, above-mentioned composite construction particle Content compared with above-mentioned 100 mass parts of resinoid bond in the range of 50~250 mass parts.Hereinafter, to most surface layer Each inscape (constituent) illustrates.

＜ composite construction particles ＞

The composite construction particle formed contained by the layer of the most surface of Electrophtography photosensor be core for inorganic particulate and The composite construction particle that coating is formed doped with the tin oxide of aluminium (Al) on above-mentioned inorganic particulate.

(core：Inorganic particulate)

The core for forming above-mentioned composite construction particle is inorganic particulate.It, can be right by using inorganic particulate in core Most surface layer assigns mechanical strength, improves case hardness, and the wearability of most surface layer, scratch resistance improve.And then preferably may be used To inhibit the inorganic particulate that the residual electric potential on the surface of most surface layer rises, iconic memory generates.In addition, from relative dielectric constant From the perspective of small, static characteristic, the inorganic particulate preferably have can ensure that most surface layer charging property it is such the advantages of.Into And it is preferably that proportion is small, the stability-enhanced inorganic particulate of manufacture that is not precipitated in coating fluid, can make most surface layer.Make For above-mentioned inorganic particulate, as described above, from the viewpoints such as mechanical strength are assigned, for example, barium sulfate (BaSO can be enumerated₄), two Silica (silica；SiO₂), aluminium oxide (alumina；Al₂O₃), titanium oxide (titania；TiO₂), zinc oxide (ZnO), oxygen Change copper (CuO), cerium oxide (ceria；CeO₂) etc..They can be used alone or two or more kinds may be used.In addition, this Commercially available product that can be used can also use composite for a little inorganic particulates.Inorganic particulate preferably as described below.That is, composite construction Particle is the electroconductive particle for showing n-type conductivity.Positive charge can not eliminate the negative electrical charge inside the electroconductive particle of n-type.Cause This, the charge on electroconductive particle needs to be supported on electroconductive particle surface.Therefore, the core used in composite construction particle is excellent It elects the inorganic particulate without electric conductivity as, and is preferably BaSO from the perspective of the transparency after most surface layer film forming₄、 SiO₂、Al₂O₃.It is, for example, 10 that " not having electric conductivity " mentioned here, which refers to resistivity,¹²More than Ω cm.In addition, as core The resistivity of inorganic particulate can measure in the same manner as the volume resistivity of aftermentioned composite construction particle.

(average grain diameter of the primary particle of inorganic particulate)

As described above in order to assign mechanical strength and then maintain electrical characteristics, reduce point of discharge and be put into the big particle of grain size, Spark location is reduced, from such a viewpoint, the average grain diameter of the primary particle of the inorganic particulate as above-mentioned core is excellent Elect 30~200nm as, more preferably the model of 50~200nm, further preferably 50~180nm, particularly preferably 80~150nm It encloses.It will not become if more than 30nm, preferably more than 50nm, the then amount of the inorganic particulate contained in the most surface layer of photoreceptor It (is being excessively 50~250 mass compared with composite construction particle of 100 mass parts of resinoid bond using inorganic particulate as core to obtain In the range of part), it is possible to reduce spark location.Therefore, it is excellent in terms of it can assign sufficient film-strength to electric discharge.If The average grain diameter of the primary particle of inorganic particulate is below 200nm, is preferably below 180nm, then in the most surface layer of photoreceptor The content of inorganic particulate will not become very few, it is excellent in terms of it can fully meet as the electrical characteristics of photoreceptor.In addition, The average grain diameter (average primary particle diameter) of the primary particle can pass through the volume reference grain size of the particle based on laser diffractometry It measures to be measured.In addition, other particles, for example, average grain diameter (the average once grain of the primary particles such as composite construction particle Footpath) it can also measure as described above.

(compared with the content of the inorganic particulate of composite construction particle total amount)

The content of inorganic particulate is preferably 20~90 mass % compared with composite construction particle total amount, and more preferably 30~70 Quality %.If the scope, then effect of the invention can effectively be obtained.In addition, " composite construction mentioned here Particle " refers to the form that the most surface layer in photoreceptor contains.For example, aftermentioned surface treatment and/or fluorine tree are carried out In the case that fat is coated, having carried out the composite construction particle of surface treatment and/or fluororesin coating becomes object.In addition, not into Row these surface treatment and/or fluororesin be coated in the case of, be not surface-treated and/or fluororesin coating composite construction Particle becomes object.

(being coated in the tin oxide doped with aluminium on inorganic particulate)

Be coated on the inorganic particulate (core) for forming above-mentioned composite construction particle doped with aluminium tin oxide (it is following, Also referred to as " mix Al tin oxide ") inorganic particulate (core) can be made to the indefatigable composite construction particle that discharges, pass through Containing the particle, discharge deterioration during roller strap electricity, excellent in abrasion resistance are can inhibit, and good image can be imaged as.

(doping of aluminium)

Be coated above-mentioned inorganic particulate mix Al tin oxide compared with the aluminium (Al) of 100 mass parts of tin oxide doping for example For the scope of 0.05~1 mass parts, preferably 0.05~0.5 mass parts.It, can be with by the way that the doping of Al is set to above range Meet as electrical characteristics necessary to photoreceptor.If the doping of Al is more than 0.05 mass parts, the body of composite construction particle Product resistivity will not become too low, excellent in terms of it can keep charge.On the other hand, if the doping of Al for 1 mass parts with Under, then the volume resistivity of composite construction particle will not become excessively high, with can making charge good (smooth) by, Ke Yichong The aspect for getting the necessary current potential after exposure is excellent.Fluorescent X-ray can be passed through by mixing the doping of the Al in Al tin oxide Analytical equipment etc. is measured.

(the forming method of composite construction particle：Method including adulterated al)

As the forming method (method for being included in doping Al in tin oxide) of composite construction particle, it is not particularly limited, It can be appropriately used known method.For example, composite construction particle can pass through following forming method (1), formation side Method (2) manufactures.

The forming method (1) of composite construction particle

The manufacturing method of the composite construction particle has following process：

The inorganic particulate as core will be made to disperse the slurry formed in media as well to mix with tin source compound,

PH adjustings are carried out to the mixed slurry of gained and the Surface Creation in above-mentioned inorganic particulate (core) includes the heavy of tin Starch, manufacture sediment attachment particle,

Aluminum source compound is added in above-mentioned mixed slurry, which is supplied above-mentioned sediment adheres to particle,

The process that above-mentioned sediment attachment particle is calcined,

In the process of the above-mentioned sediment of Surface Creation of above-mentioned inorganic particulate (core), with homogenizer to above-mentioned mixing slurry Material applies shearing force or irradiates ultrasonic wave to above-mentioned mixed slurry.

The forming method (2) of composite construction particle

The inorganic particulate as core will be made to disperse the slurry formed in media as well and tin source compound and aluminum source compound Mixing,

PH adjustings are carried out to the mixed slurry of gained and the Surface Creation in above-mentioned inorganic particulate (core) includes tin and aluminium Co-precipitate, manufacture co-precipitate attachment particle,

The process that above-mentioned co-precipitate attachment particle is calcined,

In the process of the above-mentioned co-precipitate of Surface Creation of above-mentioned inorganic particulate (core), with homogenizer to above-mentioned mixing Slurry applies shearing force or irradiates ultrasonic wave to above-mentioned mixed slurry.

First, the forming method (1) of composite construction particle is illustrated.In this forming method, first, it will make as core The inorganic particulate of material disperses the slurry formed in media as well and is mixed with tin source compound.The compounding ratio of water and core in slurry It is compared with 1 liter of water, core is preferably 10g~100g, further preferably 30g~80g.If the compounding ratio of the two is the model In enclosing, then the coil serving or coating of uniform tin oxide are easy to get.As tin source compound, it is, for example, possible to use water-soluble Property tin compound.As water-soluble tin compound, as long as the sediment comprising tin can be made to be attached to the surface of core, do not have It is particularly limited to.For example, sodium stannate, butter of tin etc. can be used.Pass through the water in the mixed slurry being obtained by mixing of the two Compounding ratio with tin source compound is that the Sn concentration in the tin source compound compared with water is preferably the matter of 1 mass %~20 Measure %, further preferably the mass % of 3 mass %~10.If the compounding ratio of the two is in the range of being somebody's turn to do, to be easy to get uniformly Tin oxide coil serving or coating.

Then, the pH for being added the mixed slurry of tin source compound is adjusted.PH adjust by add acid or alkali come into Row.It adjusts to carry out the neutralization reaction of tin source compound by the pH.As the method for carrying out neutralization reaction, can enumerate in slurry Middle addition acidic materials, the method for alkaline matter.As acidic materials, such as sulfuric acid, nitric acid, acetic acid etc. can be enumerated.Use sulphur When sour, if being used with the state of dilute sulfuric acid, the coil serving or coating of uniform tin oxide are easy to get.The concentration of dilute sulfuric acid Usually 10~50 capacity %.As alkaline matter, such as sodium hydroxide, ammonium hydroxide etc. can be enumerated.Among these, sodium hydroxide by In easily management concentration, therefore be preferred.By the neutralization reaction of tin source compound, tin is included in the Surface Creation of above-mentioned core Sediment, can obtain sediment attachment particle.The pH of mixed slurry after neutralization is preferably 0.5~5, and more preferably 2~4, Further preferably 2~3.

The neutralization reaction for carrying out tin source compound is adjusted by the pH of mixed slurry, tin is included in the Surface Creation of core During sediment, it is favourable to apply shearing force to mixed slurry with homogenizer or irradiate ultrasonic wave to mixed slurry.Pass through progress This operation inhibits the decline of the crystallite diameter of tin oxide caused by adding aluminium, and it is excellent to can obtain environment resistant (wearability) Composite construction particle.When applying shearing force to mixed slurry with homogenizer and during irradiation ultrasonic wave, it is preferred to use using following A part for endless path is provided with the reaction unit of homogenizer or ultrasonic vibrator, makes in the circulating path comprising tin source The mixed slurry Xun Huan of object is closed, while acidic materials or alkaline matter are added in the installation position of homogenizer or ultrasonic vibrator Method.Alternatively, it is also preferred that in mother liquor tank set ultrasonic vibrator and to mixed slurry direct irradiation ultrasonic wave.

When using homogenizer, mixing speed is preferably more than 5000rpm, particularly preferably more than 10000rpm.Stirring The upper limit value of speed is not particularly limited, more high the more preferred, if carrying out high-speed stirred in 16000rpm or so, effectively inhibits The reduction of the crystallite diameter of tin oxide caused by adding aluminium can obtain environment resistant (wearability) excellent composite construction grain Son.When on the other hand, using ultrasonic vibrator, ultrasonic frequency is preferably set to 10kHz~10MHz, is particularly preferably set to 20kHz~5MHz is particularly preferably set to 20kHz~50kHz, and ultrasonic power output preferably is set to 50W~20kW, especially excellent Choosing is set to 500W~4000W.

A part in circulating path is provided with the reaction unit of homogenizer or ultrasonic vibrator, such as can be used Device recorded in Japanese Unexamined Patent Publication 2009-255042 publications and Japanese Unexamined Patent Publication 2010-137183 publications.

The neutralization reaction of tin source compound is carried out in this way, and the surface attachment obtained in core has the heavy of tin compound The particle (also referred to as sediment attachment particle) of starch.Next, adding aluminum source compound in mixed slurry, it is heavy that aluminium is supplied Starch adheres to particle.As aluminum source compound, it is preferable to use water soluble compounds.The compound can be added with the state of aqueous solution Add, alternatively, can also be added with the state of solid and it is made to be dissolved in mixed slurry.As aluminum source compound, such as can make With aluminium chloride (or its hydrate).

After adding aluminum source compound in mixed slurry, stirring of the mixed slurry etc. is carried out, aluminium is made to be attached to sediment Adhere to the surface of particle.Aluminium is with the state attachment or attached with the state of the precipitations such as hydroxide, hydroxyl hydroxide of its ion It.PH adjustings can also be carried out with acid or alkali when being difficult to adhere to, promote attachment.

The surface for obtaining core in this way is coated the precursor of the composite construction particle formed by the sediment comprising tin That is sediment attachment particle.Then, which is washed with water.Make cleaned precursor dry after dewatering and filtering.

Dry precursor is supplied to calcination process.As calcination atmosphere, reducing atmosphere, inert atmosphere or oxygen can be used Change atmosphere.If using reducing atmosphere, target composite construction particle can be obtained under relatively low calcining heat.On the other hand, During using inert atmosphere or oxidizing atmosphere, calcining heat is preferably set higher compared with the situation for using reducing atmosphere.Especially If it is using reducing atmosphere, due to the interaction of the aluminium with containing in above-mentioned sediment, Al tin oxide can will be mixed Crystallite diameter is easily set at preferred scope (5~20nm).As reducing atmosphere, for example, can enumerate containing less than explosion limit Concentration hydrogen blanket of nitrogen.The concentration of hydrogen in blanket of nitrogen containing hydrogen is the concentration less than explosion limit, i.e. is preferably The volume % of the volume % of 0.1 volume %~10, further preferably 1 volume %~3.If the concentration of hydrogen is in the range of being somebody's turn to do, will not Tin is made to be reduced into metal, the reduction of the crystallite diameter of tin oxide caused by adding aluminium is effectively inhibited, can obtain environment resistant (wearability) excellent composite construction particle.In addition, the crystallite diameter for mixing Al tin oxide is measured by following method.That is, make XRD determining (condition is carried out with X-ray diffraction device Ultima IV (Co., Ltd.'s Rigaku systems)：X-ray CuK α, 40kV, 50mA, 20 °≤2 θ≤100 ° of measurement range, radiographic source：CuK α, scan axis：2 θ/θ, assay method：FT, digit： Counts, step width：0.01 °, gate time：10 seconds, divergent slit：2/3 °, dissipate vertical limitation slit：10mm, scatter slit： 2/3 °, receive slit：0.3mm, monochrome receive slit：0.8mm), then, read in and surveyed using the analysis software PDXL of Rigaku Fixed number evidence (uses SnO₂ICDD cards：00-046-1088), can crystallite be carried out by Halder-Wagner methods after precise treatment The calculating (being maked corrections using external perimysium reference sample into line width, analysis object is crystallite diameter and lattice strain) of diameter.

When using reducing atmosphere, calcining heat is preferably greater than 400 DEG C and for less than 1200 DEG C, and further preferably 500 DEG C~900 DEG C.During using inert atmosphere or oxidizing atmosphere, it is preferred to use 150 DEG C higher than the temperature or more of calcining heat.It forges Burn the time using calcining heat as above range in for condition, be preferably 5 minutes~60 minutes, further preferably 10 minutes~30 Minute.If calcination condition draws for that in the range of these, can be effectively inhibited while tin oxide is prevented to be sintered because adding aluminium The reduction of the crystallite diameter of the tin oxide risen, obtains environment resistant (wearability) excellent composite construction particle.

Then, the forming method (2) of composite construction particle is illustrated.In this forming method, it will make as core Inorganic particulate disperse aspect and shape that the slurry formed in media as well is mixed with tin source compound and aluminum source compound this three It is different into method (1).This three is mixed and adjusts the pH of mixed slurry, so as to include tin and aluminium in the Surface Creation of core Co-precipitate obtains co-precipitate attachment particle.Then, in the process for generating the co-precipitate, with homogenizer to mixing Slurry applies shearing force or irradiates ultrasonic wave to above-mentioned mixed slurry.Co-precipitate attachment particle and the forming method (1) of gained Situation similarly calcined.Target composite construction particle is obtained in this way.

(utilizing the coating mode for mixing Al tin oxide)

In addition, using mixing the coating of Al tin oxide within the scope of the effect of the invention in the range of effect, can (1) using as core The surface of the inorganic material of material completely without expose mode exhaustive be continuously coated the surface, can also (2) using as The mode that a surface part for the inorganic material of core is exposed discontinuously is coated the surface.In general, Fig. 4 (b) institutes as be described hereinafter Show, be the mode of the latter.This is because particle shape (or discoid) mix Al tin oxide be coated in the form of being in contact with each other it is inorganic The surface of material, therefore the part that the part of the surface with inorganic material is exposed.

(mixing the content that the thickness of Al tin oxide is replaced)

Mix Al tin oxide coil serving (above-mentioned (2) discontinuous coating in the case of) or coating (above-mentioned (1) it is continuous In the case of coating) as long as thickness fully demonstrate the coil serving or coating electric conductivity degree, then without exceedingly It thickens.If the thickness conversion of coil serving or coating is represented into the amount of tin oxide, mix the content of Al tin oxide compared with Composite construction particle total amount is preferably 30~70 mass %, more preferably 40~60 mass %.It, then can be more if the scope Efficiently obtain the effect of the present invention.The tin of composite construction particle, the amount of aluminium can be by making the upper of composite construction particle Solution obtained from coil serving or coating are dissolved with acid is stated to be measured to be obtained with ICP luminescence spectrometer analyzers.In addition, this In described " composite construction particle " refer to the form that the most surface layer in photoreceptor contains.For example, it carries out aftermentioned Surface treatment and/or fluororesin be coated when, carried out surface treatment and/or fluororesin coating composite construction particle become pair As.In addition, when not carrying out these surface treatments and/or fluororesin coating, it is not surface-treated and/or what fluororesin was coated answers Closing structured particles becomes object.

(average grain diameter of the primary particle of composite construction particle)

As described above in order to assign mechanical strength and then maintain electrical characteristics, reduce point of discharge and be put into the big particle of grain size, Reduce spark location, from such a viewpoint, the average grain diameter of the primary particle of above-mentioned composite construction particle for 50~ 200nm is preferably the scope of 80~150nm, more preferably 100~120nm.If the primary particle of composite construction particle is averaged Grain size is less than 50nm, then the amount for the composite construction particle that the most surface layer of photoreceptor contains largely exists (glues compared with resin In the range of 100 mass parts of agent are tied as the composite construction particle of 50~250 mass parts), point of discharge largely exists.Therefore, for Electric discharge, film (most surface layer) strength deterioration.If the average grain diameter of the primary particle of composite construction particle is more than 200nm, most table The content of the composite construction particle of surface layer tails off, and can not meet the electrical characteristics as photoreceptor.In addition, the primary particle is averaged Grain size (average primary particle diameter) can be measured by the volume reference particle size determination of the particle based on laser diffractometry.This one The measure of the average grain diameter (average primary particle diameter) of secondary particle is either with or without surface treatment and/or fluororesin coating all to being not carried out The composite construction particle of the state of these surface treatments and/or fluororesin coating is measured.

It analyzes the most surface layer of photoreceptor and calculates the average grain diameter (the equal primary particle size of number) of the primary particle of inorganic particulate When, it can calculate in the following manner.Scanning electron microscope (Jeol Ltd.'s system) can be utilized to photoreceptor The section of most surface layer shoots 10000 times of enlarged photograph, will utilize 300 composite construction particles of scanner random read take and The photograph image (not including aggregated particle) obtained uses automated graphics processing resolver LUZEX AP (Co., Ltd. NIRECO System) and Software version Ver.1.32 calculatings.In this case, (number is once for the average grain diameter of the primary particle Grain size) measure also whether there is surface treatment and/or fluororesin coating all to be free of by these surface treatment and/or fluororesin The composite construction particle (inorganic matter) for being coated obtained process film or film (organic matter) part is measured.

(volume resistivity of composite construction particle)

It is, for example, 10 at 25 DEG C that the volume resistivity of composite construction particle, which is,¹~10⁸Ω cm are preferably 1.0 × 10⁴~ 9.9×10⁷Ω cm, more preferably 1.0 × 10⁵~9.9 × 10⁶The scope of Ω cm.By the way that volume resistivity is set to above-mentioned model It encloses, can meet as electrical characteristics necessary to photoreceptor.If volume resistivity is 10¹More than Ω cm, then composite construction particle The sheet resistance of film (coating inorganic particulate mix Al tin oxide) will not become too low, the side of sufficient charge can kept Face is excellent.On the other hand, by the way that volume resistivity is set to 10⁸Below Ω cm, the sheet resistance of composite construction particle will not become Must be excessively high, it is excellent in terms of the necessary current potential after charge being made to be accurately passed through, can be exposed.Volume resistivity Measure for example using press-powder resistance measurement system (Mitsubishi Chemical PD-41) and determination of resistivity device (Mitsubishi Chemical MCP-T600) into Row.Sample (composite construction particle) 15g is put into probe tube, probe unit is fixed on PD-41.It is measured using MCP-T600 Apply 500kgf/cm using hydraulic jack²Resistance value during pressure.Press-powder is calculated by the resistance value and sample thickness that are measured Resistance (volume resistivity).As the opportunity of measure, as long as to the composite construction particle that contains in the most surface layer of photoreceptor Mode carries out.For example, be not surface-treated and/or fluororesin be coated when, as long as formed do not carry out these processing It is measured after composite construction particle.In addition, it is surface-treated after composite construction particle is formed (at silane coupling agent Reason) and/or fluororesin be coated when, as long as surface treatment (silane coupling agent processing) and/or fluororesin be coated after be measured .Assay method either which kind of mode can be carried out unchangeably.

(content of composite construction particle)

The layer (most surface layer) for forming the most surface of photoreceptor also contains tree in addition to containing above-mentioned composite construction particle During fat binding agent, the content of the composite construction particle is preferably 50~250 mass parts compared with 100 mass parts of resinoid bond The scope of scope, more preferably 70~200 mass parts.If the scope, then effect of the invention can effectively be obtained Fruit.If composite construction particle is more than 50 mass parts compared with resinoid bond, the sufficient patience to electric discharge can be obtained.Into And the presence in the electric conductivity portion (=composite construction particle) as charge path in most surface layer will not become very few, it can be with The passability for being effectively prevented charge is deteriorated, and can obtain necessary current potential after exposure.On the other hand, if 250 mass parts Hereinafter, then composite construction particle will not excessively exist in most surface layer, the increase of the number of point of discharge when can inhibit to discharge, It is effectively prevented the decline of the patience for electric discharge.In addition, " composite construction particle " mentioned here refers in photoreceptor most The form that superficial layer contains.For example, when having carried out aftermentioned surface treatment and/or fluororesin coating, carry out at surface Reason and/or the composite construction particle of fluororesin coating become object.In addition, these surface treatments and/or fluororesin quilt are not carried out When covering, it is not surface-treated and/or the composite construction particle of fluororesin coating becomes object.

(the composite construction particle being surface-treated with surface conditioning agent)

From the perspective of dispersiveness, above-mentioned composite construction particle is preferably surface-treated with surface conditioning agent, into And more preferably to have the surface conditioning agent of reactive organic group to be surface-treated.

As surface conditioning agent, it is preferable to use with the surface of composite construction particle before treatment existing for the reactions such as hydroxyl Surface conditioning agent, as these surface conditioning agents, silane coupling agent, titanium coupling agent etc. can be enumerated.

In addition, in the present invention, for the purpose of the hardness of most surface layer for further improving photoreceptor, it is preferable to use with anti- The surface conditioning agent of answering property organic group, more preferably using the surface treatment that reactive organic group is polymerism reactive group Agent.It is the poly- of following polymerizable compounds in resinoid bond by using the surface conditioning agent with polymerism reactive group It is also reacted when closing solidfied material (solidified resin) with the polymerizable compound, therefore firm protective film can be formed.

As the surface conditioning agent with polymerism reactive group, it is however preferred to have acryloyl group or methylacryloyl Silane coupling agent.By implementing surface treatment, composite construction with the surface conditioning agent containing acryloyl group or methylacryloyl Particle can form firm most surface layer with covalent bonding via resinoid bond and surface conditioning agent.As this tool There is the surface conditioning agent of polymerism reactive group, well known compound as described below can be illustrated.

As the silane coupling agent with acryloyl group or methylacryloyl, can illustrate such as following compounds.

S1：CH₂=CHCOO (CH₂)₂Si(CH₃)(OCH₃)₂

S2：CH₂=CHCOO (CH₂)₂Si(OCH₃)₃

S3：CH₂=CHCOO (CH₂)₂Si(OC₂H₅)(OCH₃)₂

S4：CH₂=CHCOO (CH₂)₃Si(OCH₃)₃

S5：CH₂=CHCOO (CH₂)₂Si(CH₃)Cl₂

S6：CH₂=CHCOO (CH₂)₂SiCl₃

S7：CH₂=CHCOO (CH₂)₃Si(CH₃)Cl₂

S8：CH₂=CHCOO (CH₂)₃SiCl₃

S9：CH₂=C (CH₃)COO(CH₂)₂Si(CH₂)(OCH₃)₂

S10：CH₂=C (CH₃)COO(CH₂)₂Si(OCH₃)₃

S11：CH₂=C (CH₃)COO(CH₂)₃Si(CH₃)(OCH₃)₂

S12：CH₂=C (CH₃)COO(CH₂)₃Si(OCH₃)₃

S13：CH₂=C (CH₃)COO(CH₂)₂Si(CH₃)Cl₂

S14：CH₂=C (CH₃)COO(CH₂)₂SiCl₃

S15：CH₂=C (CH₃)COO(CH₂)₃Si(CH₃)Cl₂

S16：CH₂=C (CH₃)COO(CH₂)₃SiCl₃

S17：CH₂=CHCOOSi (OCH₃)₃

S18：CH₂=CHCOOSi (OC₂H₅)₃

S19：CH₂=C (CH₃)COOSi(OCH₃)₃

S20：CH₂=C (CH₃)COOSi(OC₂H₅)₃

S21：CH₂=C (CH₃)COO(CH₂)₃Si(OC₂H₅)₃

S22：CH₂=CHCOO (CH₂)₂Si(CH₃)₂(OCH₃)

S23：CH₂=CHCOO (CH₂)₂Si(CH₃)(OCOCH₃)₂

S24：CH₂=CHCOO (CH₂)₂Si(CH₃)(ONHCH₃)₂

S25：CH₂=CHCOO (CH₂)₂Si(CH₃)(OC₆H₅)₂

S26：CH₂=CHCOO (CH₂)₂Si(C₁₀H₂₁)(OGH₃)₂

S27：CH₂=CHCOO (CH₂)₂Si(CH₂C₆H₅)(OCH₃)₂

As surface conditioning agent, in addition to above-mentioned chemical formula S1 to S27, the tool that may be polymerized reaction can also use There is the silane compound of reactive organic group.These surface conditioning agents may be used alone or in combination two or more.This Outside, such surface conditioning agent can use composite, can also use commercially available product.As commercially available product, such as SHIN-ETSU HANTOTAI can be enumerated Silane coupling agent KBM-502, KBM-503, KMB-5103, KBE-503 of chemical industry Co. Ltd. system etc., but it is not limited to it .

The usage amount of surface conditioning agent is not particularly limited, excellent compared with 100 mass parts of composite construction particle of before processing Elect 0.1~100 mass parts as.Composite construction particle is stated preferably with compared with the composite construction particle of before processing i.e., it is possible to say 100 mass parts are surface-treated (formation Surface Treated Films) for the surface conditioning agent of the scope of 0.1~100 mass parts.Into And above-mentioned composite construction particle is more preferably using 100 mass parts of composite construction particle compared with before processing as 0.5~10 mass parts The surface conditioning agent with polymerism reactive group of scope be surface-treated (formation Surface Treated Films).If the model It encloses, then can effectively obtain the effect of the present invention.If the surface conditioning agent with polymerism reactive group compared with 100 mass parts of composite construction particle of before processing is more than 0.5 mass parts, then resinoid bond and composite construction grain when curing Cross-linked structure can be formed between son, is preferred.On the other hand, if the surface conditioning agent with polymerism reactive group compared with 100 mass parts of composite construction particle of before processing are below mass part for 10, then do not remain extra surface treatment in superficial layer Agent does not influence image quality, is preferred.In addition, " the composite construction particle of before processing " refer to not carry out using surface conditioning agent, The composite construction particle of the state of surface treatment or the coating of fluororesin etc..In addition, silane coupling agent (surface conditioning agent), fluorine tree Fat and its usage amount (contents of Surface Treated Films or fluororesin film from silane coupling agent or fluororesin) can be removed photosensitive The most surface layer of body, is analyzed using x-ray photoelectron optical spectroscopy.

(surface treatment method using surface conditioning agent of composite construction particle)

Specifically, the surface treatment of composite construction particle can carry out in the following way：By answering comprising before processing The slurry (suspension of solids) for closing structured particles and surface conditioning agent carries out case of wet attrition, so as to make composite construction grain The surface treatment of particle is carried out while sub- miniaturization, thereafter, removes solvent and powder.

Slurry is preferably using the 100 mass of surface inorganic agent of composite construction particle compared with before processing as 0.1~100 mass Part, solvent mix for the ratio of 50~5000 mass parts.

In addition, as the device used in the case of wet attrition of slurry, wet media decentralized device can be enumerated.Wet media Decentralized device is the device for having following process：Pearl is filled in container as medium, and then, make with rotation axis vertically The agitator disk of installation rotates at a high speed, crushes scattered process so as to the aggregated particle of broken P-type semiconductor particle, makees It is formed for it, as long as when being surface-treated to composite construction particle composite construction particle can be made fully to disperse, and energy The form being enough surface-treated just has no problem, for example, vertical horizontal, the various patterns such as continous way batch-type.Specifically For, sand mill, super viscous mill (Ultra Visco Mill), ball mill, Green can be used to grind (Glen Mill), Dai Nuomo (Dyno mill), agitator mill (Agitator Mill), dynamic mill (Dynamic Mill) etc..These decentralized devices use Ball, pearl etc. crush that medium (medium) is damaged by pressure, rubs, sheared by impact, shear stress etc. carries out Crushing of Ultrafine and scattered.

As the pearl used in wet media decentralized device, can use with glass, aluminium oxide, zircon, zirconium oxide, The ball as raw material such as steel, flint, particularly preferably using zirconium oxide system, zircon system, the pearl for aoxidizing aluminum.In addition, conduct The size of pearl, in general, the pearl of 1~2mm of diameter or so can be used, it is preferable to use the pearls of 0.1~1.0mm or so in the present invention Son.

The disk or container inner wall used in wet media decentralized device can use stainless steel, nylon system, ceramic system Etc. the disk or container inner wall of various raw materials, but disk made of ceramics or appearance as particularly preferred zirconium oxide or carborundum in the present invention Device inner wall.

(the composite construction particle being coated by fluororesin)

Above-mentioned composite construction particle is preferably coated by fluororesin, and then, more preferably surface is carried out with above-mentioned surface conditioning agent After processing, it is coated by fluororesin.As with the effect of fluororesin coating composite construction particle, the fluorine tree high by imposing insulating properties Fat can improve patience of the composite construction particle (electroconductive particle) to electric discharge, can inhibit because of the electric discharge of composite construction particle Hydrophiling caused by deterioration.The inhibition of hydrophiling can not only improve electric discharge patience, but also also contribute to improve the holding of charge Property, it helps the raising of the filament characteristic under hot and humid.

It as fluororesin, is not particularly limited, known fluororesin can be used.It for example, can be with Japanese Unexamined Patent Publication The beta-unsaturated esters monomer made containing fluorine aliphatic group recorded in 2002-146271 publications with comprising unsaturated silane monomer The form (form of fluororesin) of copolymer that forms of monomer copolymerization use, can also be with the coating compositions comprising the copolymer The form (form of smears) of object uses.It alternatively, can be with (methyl) recorded in Japanese Unexamined Patent Publication 2013-028807 publications The form (form of fluororesin) of fluoroalkyl base ester/(methyl) acrylic copolymer uses, can also be to include the copolymerization The form (form of smears) of the coating composition of object and the solvent being partly fluorinated uses.At this point, above-mentioned fluoroalkyl has 6 A following carbon atom, moreover, when above-mentioned fluoroalkyl is perfluoroalkyl, above-mentioned copolymer can be used comprising below 5 weight % (methyl) acrylic acid copolymer.It is preferably such as (first as the fluororesin contained by the form of these fluororesin or smears Base) fluoroalkyl base ester/(methyl) acrylic copolymer includes the fluororesin of fluorinated methyl acrylate copolymer segment like that. This is because by the way that fluororesin is made to include fluorinated methyl acrylate copolymer segment, above-mentioned composite construction can be further improved The coating effect brought by fluororesin of particle.But the fluororesin (form for including smears) used in the present invention is unlimited In above-mentioned fluororesin.Composite can be used in such fluororesin (form for including smears), can also use commercially available product.As Commercially available product, such as fluorine system smears Novec (registered trademark) 2702, Novec1700, Novec1720 of 3M company systems can be enumerated Deng, but it is not limited to them.As described above, fluorine system smears Novec (registered trademark) 2702 grade fluororesin (smears) fluorine removal tree Also comprising solvent beyond fat, as shown in the Examples, by by composite construction particle and fluororesin (Novec (registered trademark) 2702 Deng) mixed (=also carried out drying, solvent remove), (formation fluororesin film) fluorine can be coated on composite construction particle Resin.

The usage amount of fluororesin (form for including smears) is not particularly limited, compared with the composite construction grain of before processing Sub 100 mass parts are preferably the scope of the scope, more preferably 1~10 mass parts of 0.1~100 mass parts.I.e., it is possible to it says It is preferably preferably 0.1~100 mass parts compared with 100 mass parts of composite construction particle of before processing to state composite construction particle The fluororesin coating (formation fluororesin film) of scope, the more preferably scope of 1~10 mass parts.It, then can be more if the scope Added with the effect for efficient obtaining the present invention.If fluororesin is 1 matter compared with " the composite construction particle of before processing " 100 mass parts It measures more than part, then can fully obtain the surface coating property of composite construction particle, composite construction particle during electric discharge can be inhibited The hydrophiling on surface.Therefore, even if under hot and humid environment, it also can fully keep charge and good figure can be formed Picture.In addition, it is below mass part if 10, then the coating to composite construction particle can be fully obtained, can be effectively inhibited The passability of charge caused by the high fluororesin of insulating properties is deteriorated.Therefore, can fully be obtained after photoreceptor exposure must The current potential wanted can form good image.In addition, " the composite construction particle of before processing " refers to not carry out utilizing surface treatment The composite construction particle of the state of surface treatment, the coating of agent, fluororesin etc..

(surface treatment method using fluororesin of composite construction particle)

It as the surface treatment carried out using fluororesin of composite construction particle, is not particularly limited, can be used previous public The method known.For example, the coating composition recorded in Japanese Unexamined Patent Publication 2002-146271 publications can be used (for the shape of fluororesin Formula, the form of smears) coating method (coating method), can also be remembered using Japanese Unexamined Patent Publication 2013-028807 publications The coating method of the coating composition (form of form, smears for fluororesin) of load.

(composition of composite construction particle)

Fig. 4 is contained in the layer of the composition most surface for the Electrophtography photosensor for representing the image forming apparatus of the composition present invention The explanation sectional view of one example of the composition of some composite construction particles and its particle structure of manufacturing process.Fig. 4 (a) is It represents that the explanation of an example of the inorganic particulate structure as core prepared in the manufacturing process of composite construction particle is used to cut Face figure.Fig. 4 (b) is to represent to be coated the composite construction particle formed doped with the tin oxide of aluminium on the inorganic particulate of Fig. 4 (a) The explanation sectional view of one example of structure.Fig. 4 (c) be represent by the composite construction particle of Fig. 4 (b) with surface conditioning agent into The explanation sectional view of one example of the structure for the composite construction particle that row surface treatment forms.Fig. 4 (d) is represented Fig. 4 (c) the composite construction particle that the composite construction particle being surface-treated with surface conditioning agent is formed with fluororesin coating The explanation sectional view of one example of structure.Fig. 4 (a) represents the section of the inorganic particulate 21 used in core.Fig. 4 (b) institutes Show that coating is answered doped with what the tin oxide (mixing Al tin oxide) 23 of aluminium formed on core (inorganic particulate) 21 in the form shown Close 25 section of structured particles.Form as shown in Fig. 4 (b), composite construction particle of the invention may not also be aoxidized with mixing Al Tin 23 is coated core (inorganic particulate) 21 whole surface.In the present invention, the composite junction can be contained in the most surface layer of photoreceptor Structure particle 25 can also contain the following composite construction particle being surface-treated.It is shown in form shown in Fig. 4 (c) 25 surface of composite construction particle of Fig. 4 (b) is carried out the composite construction particle 25a that surface treatment forms with surface conditioning agent to cut Face.On above-mentioned 25 surface of composite construction particle, except coating inorganic particulate 21 mix 23 surface of Al tin oxide in addition to, also comprising nothing (mix 23 coil serving of Al tin oxide (shot-like particle) mutual gap etc.) in 21 surface of machine particle.Pass through above-mentioned surface treatment, composite junction Structure particle 25 (inorganic particulate 21 and coating inorganic particulate 21 mix Al tin oxide 23) surface is coated by above-mentioned surface conditioning agent (forming Surface Treated Films 27).It is shown in form shown in Fig. 4 (d) by the composite construction grain being surface-treated of Fig. 4 (c) Sub- 25a (inorganic particulate 21 and 4 (c) being surface-treated of 4 (c) be surface-treated mix Al tin oxide 23 Surface etc.) the composite construction particle 25b sections that are formed with fluororesin coating.It is coated by fluororesin, 4 (c's) has carried out table The composite construction particle 25a surfaces (progress of the inorganic particulate 21 and 4 (c) being surface-treated of 4 (c) of surface treatment Surface for mixing Al tin oxide 23 of surface treatment etc.) by the coating of above-mentioned fluororesin (forming fluororesin film 29).Inorganic particulate 21 with The ratio for mixing the size of 23 coil serving of Al tin oxide (shot-like particle) 23 is set to and the actual example that is used in embodiment almost phase The ratio of same size.

(resinoid bond)

In the most surface layer of photoreceptor, in addition to above-mentioned composite construction particle, preferably further comprising resinoid bond. In addition, the content of resinoid bond is as described in above-mentioned one, composite construction particle.That is, above-mentioned composite construction particle is preferably satisfied It is the important document of the scope of 50~250 mass parts compared with 100 mass parts of resinoid bond.

Resinoid bond is preferably thermoplastic resin or light-cured resin, especially from obtaining high film-strength, More preferably light-cured resin.

As resinoid bond, for example, polyvinyl butyral resin, epoxy resin, polyurethane resin, phenolic aldehyde can be used Resin, polyester resin, alkyd resin, polycarbonate resin, organic siliconresin, acrylic resin, melmac etc..It uses It is preferably polycarbonate resin during thermoplastic resin.In addition, during using light-cured resin, preferably by will have 2 with On free-radical polymerised functional group compound (hereinafter also referred to " multifunctional free-radical polymerised compound " or " polymerism Compound ") carry out polymerisation using the irradiation etc. of ultraviolet light, electron beam isoreactivity ray obtained from solidified resin (=it is poly- The polymerizing curable object of conjunction property compound).The polymerizing curable object of polymerizable compound is because each resin glues as resinoid bond Agent (each polymerizable compound of raw material) is tied each other when curing by covalent key connection, jail can be formed as most surface tunic Solid film quality.The film so obtained has three-dimensional crosslinking structure, with the obtained most surface layer of thermoplastic resin using two dimension not Together, can have patience and the physical scratch resistance to electric discharge.The above-mentioned resin enumerated as resinoid bond can be single It solely uses a kind or two or more is applied in combination.

(multifunctional free-radical polymerised compound)

As multifunctional free-radical polymerised compound (polymerizable compound), from few light quantity or short time just It can carry out curing and set out, particularly preferably with the acryloyl group (CH of 2 or more₂=CHCO-) or methylacryloyl (CH₂ =CCH₃CO-) the acrylic monomer or their oligomer as free-radical polymerised functional group.Therefore, set as curing Fat (polymerizing curable object), the acrylic resin preferably formed using acrylic monomer or its oligomer.

As these multifunctional free-radical polymerised compounds (polymerizable compound), such as following compound can be illustrated.

Wherein, in the chemical formula for notationally stating exemplary compounds M1~M15, R represents acryloyl group (CH₂=CHCO-), R ' expression methylacryloyls (CH₂=CCH₃CO-)。

(polymerization initiator)

Polymerization initiator is obtained in manufacture by the way that above-mentioned multifunctional free-radical polymerised compound is carried out polymerisation Solidified resin (resinoid bond) during use.Polymerization initiator is to trigger multifunctional free-radical polymerised compound The radical polymerization initiator of polymerisation can enumerate thermal polymerization, Photoepolymerizationinitiater initiater etc..

As the method that multifunctional free-radical polymerised compound is made to carry out polymerisation, it can be used and cracked using electric wire The method of reaction utilizes light, hot method etc. in the presence of radical polymerization initiator.

As thermal polymerization, for example, 2 can be enumerated, 2 '-azodiisobutyronitrile, 2, double (2, the 4- diformazans of 2 '-azo Base valeronitrile), the azo-compounds such as 2,2 '-azo double (2- methylbutyronitriles)；Benzoyl peroxide (BPO), di-tert-butyl peroxide Hydrogen, tert-butyl hydroperoxide, chlorine peroxide benzoyl, dichlorobenzoyl peroxide, peroxidating bromomethyl benzoyl, the peroxidating moon Peroxide such as osmanthus acyl etc..

As Photoepolymerizationinitiater initiater, diethoxy acetophenone, 2,2- dimethoxy -1,2- diphenylethanes -1- can be enumerated Ketone, 1- hydroxy-cyclohexyl-phenyls -one, 4- (2- hydroxyl-oxethyls) phenyl-(2- hydroxyl -2- propyl) ketone, 2- benzyl -2- diformazans Base amino -1- (4- morpholinyl phenyls) butanone -1 (" Irgacure369 " (BASF Japan company systems)), 2- hydroxy-2-methyls -1- Phenyl-propane -1- ketone, 2- methyl -2- morpholinoes (4- methyl mercaptos phenyl) propane -1- ketone, 1- phenyl -1,2- propanedione -2- (O- Ethoxy carbonyl) acetophenones system or the ketal system Photoepolymerizationinitiater initiater such as oxime；Benzoin, benzoin methyl ether, benzoin ethyl ether, The benzoin ethers such as benzoin isobutyl ether, benzoin isopropyl ether system Photoepolymerizationinitiater initiater；Benzophenone, 4- hydroxy benzophenones Ketone, methyl o-benzoylbenzoate, 2- benzoyls naphthalene, 4- benzoyls biphenyl, 4- benzoyloxy phenyls ether, propylene acidifying hexichol first The benzophenone series Photoepolymerizationinitiater initiaters such as ketone, 1,4- Benzoylbenzenes；2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4- diformazans Thioxanthones system Photoepolymerizationinitiater initiaters such as base thioxanthones, 2,4- diethyl thioxanthones, bis- clopenthixal ketones of 2,4- etc..

As other Photoepolymerizationinitiater initiaters, can enumerate ethyl hydrazine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6- trimethylbenzoyl phenyl ethyoxyls phosphine oxide, double (2,4,6- trimethylbenzoyls) phenyl phosphine oxides (" Irgacure 819 " (BASF Japan company systems)), double (2,4- Dimethoxybenzoyls) -2,4,4- tri-methyl-amyls Phosphine oxide, methyl phenyl glyoxylate ester, 9,10- phenanthrene, acridine based compound, triazine based compound, imidazole compound etc..This Outside, the Photoepolymerizationinitiater initiater with photopolymerization facilitation effect can also be used alone or be used in combination with above-mentioned Photoepolymerizationinitiater initiater.Make For the Photoepolymerizationinitiater initiater with photopolymerization facilitation effect, such as triethanolamine, methyl diethanolamine, 4- dimethylaminos can be enumerated Yl benzoic acid ethyl ester, 4- dimethylaminobenzoic acids isopentyl ester, benzoic acid (2- dimethylaminos) ethyl ester, 4,4 '-dimethylamino Base benzophenone etc..

As polymerization initiator, it is preferable to use Photoepolymerizationinitiater initiaters, more preferably use alkyl phenyl ketone based compound or oxygen Change phosphine based compound, further preferably triggered using the photopolymerization with alpha-hydroxyacetophenone structure or acylphosphine oxide structure Agent.

These polymerization initiators can be used alone or be mixed with two or more.

The use ratio of polymerization initiator is 0.1~40 compared with multifunctional 100 mass parts of free-radical polymerised compound Mass parts are preferably 0.5~20 mass parts.

In the most surface layer of the photoreceptor of the present invention, except composite construction particle as described above and resinoid bond with It outside, can also be as needed containing charge agent delivery, organic fine particles, lubricant particle, antioxidant etc..

(charge agent delivery)

Charge agent delivery (charge-transporting compound) is as long as the charge with the charge carrier in conveying most surface layer is defeated Performance is sent to be not particularly limited, as charge agent delivery, such as contains the compound represented by the following general formula (1).In addition, The charge agent delivery (charge-transporting compound) used in the present invention does not have reactivity with composite construction particle.

In above-mentioned general formula (1), R¹And R²Hydrogen atom or methyl are each independently, is preferably methyl.In addition, R³For carbon number 1 ~5 straight-chain or the alkyl of branched are preferably the alkyl of carbon number 2~4.

The compound represented by above-mentioned general formula (1) is to convey the charge-transporting chemical combination of the charge carrier in most surface layer Object.Absorption is not shown in short wavelength region mostly and molecular weight is also less than 450 (being preferably 320~420), can enter most table The gap of the resin component (resinoid bond etc.) of surface layer.Therefore, it is possible to not reducing the wearability of most surface layer defeated from charge Layer is sent successfully to inject charge carrier, can hardly cause residual electric potential rise, iconic memory generate to most surface layer Surface transport charge.

R in above-mentioned general formula (1)¹And R²Hydrogen atom or methyl are each independently, but is gone out from the viewpoint of manufacture stability Hair, R¹And R²It is it is preferred that mutually different.

In addition, as the R in above-mentioned general formula (1)³The example of the straight-chain of the middle carbon number 1~5 used or the alkyl of branched Son, for example, can enumerate methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, tertiary butyl, n-pentyl, isopentyl, neopentyl, Tertiary pentyl, 2- methyl butyls etc..It is preferably propyl, normal-butyl, n-pentyl from the perspective of dissolubility among these.

The concrete example of the compound described below represented by above-mentioned general formula (1).

Above-mentioned charge agent delivery (charge-transporting compound) can be used commercially available product that composite can also be used.As by above-mentioned The synthetic method of the charges agent deliveries (charge-transporting compound) such as the compound that general formula (1) represents, can pass through well known synthesis Method synthesizes, for example, the synthetic method recorded in Japanese Unexamined Patent Publication 2006-143720 publications can be enumerated.In addition, above-mentioned charge is defeated Agent (charge-transporting compound) is sent to can be used alone or two or more is applied in combination.

In addition, the charge agent delivery (charge-transporting compound) in the most surface layer of photoreceptor is preferably with compared with resin Binding agent (polymerizing curable object) 100 mass parts contain for the ratio of 10~30 mass parts, more preferably 15~25 mass parts.Pass through Make the content ratio of charge agent delivery (charge-transporting compound) in above range, can effectively to obtain this hair Bright effect.And then the generation of image missing can be adequately suppressed.

(organic fine particles)

In the most surface layer of photoreceptor, as organic fine particles, for example, can contain comprising from melamine and benzocarbamidine The resin particles of the Component units of at least one of amine, styrene-acrylic resins particle, styrene resin beads have Machine silicon resin particles etc..They can be used alone or two or more kinds may be used.

As the above-mentioned resin for including the Component units from least one of melamine and benzoguanamine, it is specific and Speech, can enumerate the melamines such as condensation polymer, melamine and the benzoguanamine of melamine and formaldehyde and the copolymeric condensation object of formaldehyde Polyimide resin；Benzoguanamine resins such as the condensation polymer of benzoguanamine and formaldehyde etc..Among these, from toner spatter property and inhibit to scheme As the organic fine particles from the perspective of density unevenness, being preferably made of the condensation polymer of melamine and formaldehyde.

The number average primary particle diameter of these organic fine particles is preferably in the range of 0.01~5.00 μm, further preferably In the range of 0.10~3.50 μm.If in the range of this, then when forming most surface layer organic fine particles on the surface of most surface layer Expose, become larger in development with the frictional force of toner, the decline of the surface potential of photoreceptor can be inhibited.Furthermore, it is possible to make Photosensitive surface moderately surface roughening, it can be ensured that good spatter property.

(measuring method of number average primary particle diameter)

The measure of the number average primary particle diameter of organic fine particles can be obtained in the following manner.

Above-mentioned organic fine particles are existed using transmission electron microscope " JEM-2000FX " (Jeol Ltd.'s system) With 10000 times of shootings under accelerating potential 80kV, photograph image is read using scanner, uses image procossing resolver " LUZEX (registered trademark) AP " (Co., Ltd.'s NIRECO systems) carries out 2 value processing to the organic fine particles of photograph image, has for 100 Machine particle calculates horizontal direction Feret's diameter, is averaged value as number average primary particle diameter.Here, horizontal direction takes thunder The length on the side parallel with x-axis of bounding rectangle when special diameter refers to carrying out the image of organic fine particles into 2 values processing.

The content of above-mentioned organic fine particles is 5~100 mass parts compared with resinoid bond (polymerizing curable object) 100 mass parts Scope can obtain inhibiting the effect dispersed of toner, can obtain image and obscure reduced effect, therefore be preferred.In addition, from The wearability of most surface layer is preferred from the perspective of improving.

In the most surface layer of the photoreceptor of the present invention, it can further contain various antioxidants, lubricant particle.As Lubricant particle, for example, the resin particle containing fluorine atom can be enumerated, and then, as its concrete example, tetrafluoroethene tree can be enumerated Fat granule, trifluorochlorethylene resin particle, hexafluoropropene-vinyl chloride copolymer resin particle, fluoroethylene resin particle, inclined difluoro It is one kind or two or more in vinyl particle, dichlorodifluoroethylene resin particle and their copolymer particle.Wherein, preferably For tetrafluoroethylene resin particle or vinylidene fluoride resin particle.

The forming method ＞ of the most surface layer of ＜ photoreceptors

The most surface layer of the photoreceptor of the present invention can be formed in the following way：Make by composite construction particle and according to It is the polymerizable compound (raw material of the solidified resin as resinoid bond) that needs, polymerization initiator, charge agent delivery, organic The coating fluid (most surface layer coating fluid) that particle etc. mixes in a solvent, the coating solution is defeated in aftermentioned charge After sending on layer, it is dried and cured.

During above-mentioned coating, drying and curing, carry out polymerizable compound between reaction, polymerizable compound with The hydroxyl (reactive group) of composite construction particle or the composite construction particle with being surface-treated with surface conditioning agent etc. Reaction between polymerism reactive group, the interparticle reaction of the composite construction being surface-treated etc., form most surface layer.

As most surface layer with the solvent used in coating fluid, as long as composite construction particle can be made and be added as needed on Polymerizable compound (raw material of the solidified resin as resinoid bond), polymerization initiator, charge agent delivery, organic fine particles Deng dissolving or scattered, then any solvent can be used.Specifically, for example, can enumerate methanol, ethyl alcohol, normal propyl alcohol, isopropanol, N-butanol, the tert-butyl alcohol, sec-butyl alcohol, benzyl alcohol, toluene, dimethylbenzene, dichloromethane, methyl ethyl ketone, hexamethylene, ethyl acetate, Butyl acetate, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1- bis-Alkane, 1,3- dioxolanes, pyridine and diethylamine Deng, but it is not limited to them.These solvents can be used alone or two or more is applied in combination.

If the manufacturing method of coating fluid it is not also specifically limited, in a solvent add in composite construction particle and as needed Polymerizable compound (raw material of the solidified resin as resinoid bond), polymerization initiator, charge agent delivery, organic fine particles Etc. various additives and be stirred to dissolving or scattered.In addition, as long as the amount of solvent is it is not also specifically limited, will coating Liquid is suitably adjusted to fit the viscosity in painting work.

Coating method is not particularly limited, for example, Dipcoat method, spraying process can be used, spin-coating method, pearl coating, blade coating Method, electron beam rubbing method slide method well known to hopper method, circular slip hopper method etc..

It after above-mentioned coating fluid is coated with, is spontaneously dried or heated drying, after film is formed, is using polymerism chemical combination It in the case of object, irradiates active energy beam and cures, make comprising polymerizable compound (and at the surface of composite construction particle Surface conditioning agent, the fluororesin used in reason) as monomer component resin component generate.It is more excellent as active energy beam Select ultraviolet light, electron beam, further preferred ultraviolet light.

As ultraviolet light source, as long as generating the light source of ultraviolet light can use without limitation.For example, it can make With low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, flash of light (pulse) xenon Lamp etc..Irradiation condition is different according to each lamp, and ultraviolet irradiation amount is usually 5~500mJ/cm², preferably 5~ 100mJ/cm².The output power of light source is preferably 0.1~5kW, more preferably 0.5~3kW.

As the electron beam illuminating device as electron beam source, it is not particularly limited, it is however generally that, it is irradiated as electron beam Electronics accelerate (beamacceleration) machine, it is preferable to use the devices of curtain electron beam mode that is less expensive and can obtain big output power.Electricity Accelerating potential when beamlet irradiates is preferably 100~300kV.It is preferably 0.5~10Mrad as absorbed dose.

As for obtaining the irradiation time of the exposure of necessary active energy beam, being preferably 0.1 second~10 minutes, It is more preferably 0.1 second~5 minutes from the perspective of operating efficiency.

Formed photoreceptor most surface layer during, can before and after active energy beam irradiate or irradiation work It is dried in property energy-ray, the opportunity being dried can combine them and suitably select.

Dry condition can suitably be selected according to species, film thickness of solvent etc..Drying temperature is preferably 20~180 DEG C, more preferably 80~140 DEG C.Drying time is preferably 1~200 minute, more preferably 5~100 minutes.

The film thickness of the most surface layer of photoreceptor is preferably 1~10 μm, more preferably 1.5~5 μm.

(composition of photoreceptor)

Hereinafter, the composition of the Electrophtography photosensor beyond the most surface layer of photoreceptor is illustrated.

In the present invention, Electrophtography photosensor be make organic compound etc. have must not to the composition of Electrophtography photosensor The Electrophtography photosensor that the charge that can lack generates at least one of function and charge conveying function function and forms, includes institute Some is generated the photoreceptor that substance or organic charge conveying substance form by well known organic charge, is formed with high-molecular complex Charge generates photoreceptor well known to photoreceptor of function and charge conveying function etc..

The present invention photoreceptor have be sequentially laminated in conductive support body as photosensitive layer charge generation layer and Charge transport layer, the layer composition that most surface layer is laminated on the top of above-mentioned photosensitive layer.Furthermore it is preferred that conductive support body with There is interlayer between charge generation layer.

Centered on above-mentioned shown layer is formed, the composition beyond the above-mentioned superficial layer of the photoreceptor of the present invention is said It is bright.

＜ conductive support bodies ＞

The conductive support body used in the present invention can be arbitrary conductive support body as long as conductive.As Its concrete example, such as it is drum type (cylindrical shape) or the branch of sheet that can enumerate metal formings such as aluminium, copper, chromium, nickel, zinc or stainless steels Support body；The metal foil layers such as aluminium, copper are pressed on the supporter that plastic foil forms；Aluminium, indium oxide or tin oxide etc. are deposited in plastics The supporter that film forms；Conductive material is coated with individually or together with binder resin and sets the metal of conductive layer, plastics Film and paper etc..

＜ interlayers ＞

In the present invention, it can be set between conductive support body and photosensitive layer in barriers function and binding function Interbed.If it may be said that in view of preventing various failures etc., it is preferred embodiment to set interlayer.

This interlayer for example containing binder resin and electroconductive particle as needed, metal oxide particle and Into.

As the binder resin that can be used in above-mentioned conductive support body and interlayer, it is not particularly limited, it can Using known conductive support body with or interlayer binder resin.For example, casein, polyethylene can be enumerated Alcohol, NC Nitroncellulose, ethylene-acrylic acid copolymer, polyamide, polyurethane resin, gelatin etc..Among these, it is preferably The polyamide of alcohol solubility.These binder resins can be used alone or two or more is applied in combination.

For the purpose of adjusting resistance, interlayer can contain various electroconductive particles, metal oxide particle.For example, it can make With the various metal oxide particles such as aluminium oxide, zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide.And then The various electroconductive particles such as the indium oxide (ITO) doped with tin, the tin oxide (ATO) doped with antimony, zirconium oxide can also be used (ultra micron).These various electroconductive particles used for the purpose of adjusting resistance, metal oxide particle can individually make With a kind or it is mixed with two or more.When mixing two or more, the form of solid solution or fusion may be employed.

The number once grain of this various electroconductive particles used for the purpose of adjusting resistance, metal oxide particle Footpath is preferably less than 0.3 μm, more preferably less than 0.1 μm.

From the perspective of adjustment resistance, the content ratio of above-mentioned electroconductive particle and/or metal oxide particle is (total Amount) compared with 100 mass parts of binder resin in interlayer it is preferably 20~400 mass parts, more preferably 50~350 mass Part, further preferably 50~200 mass parts.

From the perspective of adjustment resistance, the film thickness in interlayer is preferably 0.1~15 μm, more preferably 0.3~10 μm.

As above interlayer can for example be formed in the following way：Binder resin is dissolved in well known solvent, As needed electroconductive particle or metal oxide particle is made to disperse and prepare interlayer formation coating fluid, by the interlayer shape Coated film is formed in the surface of conductive support body into coating solution, which is dried.

It as above-mentioned interlayer formation with the solvent used in coating fluid, is not particularly limited, for example, normal-butyl can be used Amine, diethylamide, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N,N-dimethylformamide, acetone, Methylethyl Ketone, methyl isopropyl Ketone, cyclohexanone, benzene,toluene,xylene, chloroform, dichloromethane, 1,2- dichloroethanes, 1,2- dichloros third Alkane, 1,1,2- trichloroethanes, 1,1,1- trichloroethanes, trichloro ethylene, tetrachloroethanes, tetrahydrofuran, dioxolanes, twoAlkane, Methanol, ethyl alcohol, butanol, isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide (DMSO), methyl cellosolve etc., among these, preferably Use toluene, tetrahydrofuran, dioxolanes etc..These solvents can be used alone or with mixed solvent of more than two kinds Form uses.Wherein, electroconductive particle or metal oxide particle as described above is preferably made to disperse well and is dissolved viscous Tie the solvent of agent resin, especially polyamide.Specifically, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, tertiary fourth The alcohols of the carbon numbers such as alcohol, sec-butyl alcohol 1~4 is excellent in terms of the dissolubility of polyamide and coating performance, is preferred.These are molten Agent can be used alone or two or more is applied in combination.In addition, in order to improve the dispersiveness of keeping quality and inorganic particulate, it can be simultaneously With above-mentioned solvent and cosolvent.As the cosolvent that can obtain preferred effect, benzyl alcohol, toluene, dichloromethane, ring can be enumerated Hexanone, tetrahydrofuran etc..

The concentration of binder resin in above-mentioned interlayer formation coating fluid according to film thickness, the speed of production in interlayer and Appropriate selection.

As above-mentioned electroconductive particle, the process for dispersing of metal oxide particle, ultrasonic dispersing machine, ball milling can be used Machine, sand mill and homogeneous mixer etc..

It as the coating method of interlayer formation coating fluid, is not particularly limited, such as Dipcoat method, spray can be enumerated Coating etc..

The drying means of coated film can according to the species of solvent, the film thickness in the interlayer formed and known in suitably selecting Drying means, particularly preferably carry out heated drying.

As described above, the method for forming interlayer is not particularly limited, binder resin is made to be dissolved in above-mentioned solvent, root According to need using the devices (dispersion machine) such as ultrasonic dispersing machine, ball mill, sand mill or homogeneous mixer make electroconductive particle or Metal oxide particle disperses, after preparing interlayer formation coating fluid, by the interlayer formation coating fluid in electric conductivity branch It is coated on support body with required thickness.Thereafter, be coated with layer can be made dry and complete interlayer.

＜ photosensitive layers ＞

The photoreceptor of the present invention has photosensitive layer, which has charge generation layer and charge transport layer.Specifically, Charge generation layer is stacked gradually from conductive support body side, charge transport layer forms.

《Charge generation layer》

The charge generation layer used in the photoreceptor of the present invention preferably comprises charge generation substance and binder resin is (following Also referred to as charge generation layer binder resin).

As the example of charge generation substance, for example, can enumerate the azos raw materials such as tonyred, black pigment used by women in ancient times to paint their eyebrows peace blue (diane blue), The indigo pigments such as the quinone pigments such as pyrene quinone, anthrone pile anthrone, quinoline cyanines (quinocyanine) pigment, pigment, indigo and thioindigo, Phthalocyanine colors such as polycyclic quinone pigments, the titanyl phthalocyanine pigment such as pyranthrone, two phthalyl pyrenes etc., but it is not limited to them. These charge generation substances can be used alone or two or more is applied in combination.It is preferably polycyclic quinone pigments and oxygen titanium among these Phthalocyanine color.

It as charge generation layer binder resin, is not particularly limited, well known resin can be used.It is specific as it Example, for example, polystyrene resin, polyvinyl resin, acrylic resin, acrylic resin, methacrylic resin, chlorine can be enumerated Vinyl, vinyl acetate resin, polyvinyl butyral resin, epoxy resin, polyurethane resin, phenolic resin, polyester Resin, alkyd resin, polycarbonate resin, organic siliconresin, melmac and comprising 2 in these resins with On copolymer resin (for example, vinyl chloride vinyl acetate copolymer resin, Chlorovinyl-acetate vinyl-maleic anhydride are common Copolymer resin) and polyvinyl carbazole resin etc., but it is not limited to them.These binder resins can be used alone or combine Use two or more.Preferably polyvinyl butyral resin.

Resistance is suppressed relatively low and can strongly inhibit the residual electric potential with Reusability from photoreceptor From the perspective of increase, the content ratio of the charge generation substance in charge generation layer is compared with charge generation layer with binding agent tree 100 mass parts of fat are preferably 1~600 mass parts, more preferably 20~600 mass parts, further preferably 50~500 mass Part.

The film thickness of charge generation layer according to the characteristic of charge generation substance, the characteristic of charge generation layer binder resin or Content ratio etc. and it is different, be preferably 0.01~5 μm, more preferably 0.05~3 μm, further preferably 0.1~2 μm, it is more excellent Elect 0.15~1.5 μm as.

As above the forming method of charge generation layer is not particularly limited, for example, can be formed in the following way：It is inciting somebody to action Charge generation substance is added in the solution that charge generation layer binder resin is formed with the dissolving of well known solvent, uses dispersion machine Make it scattered and prepare charge generation layer formation coating fluid.On the surface of conductive support body the charge generation layer is set to be formed In the case of the composition in setting interlayer, (coating machine is used on the surface in the interlayer with coating fluid, in conductive support body With certain film thickness) it is coated with and forms coated film, which is dried.As coating method and drying means, may be employed With the same method of method illustrated in above-mentioned superficial layer one.In addition, charge generation layer coating fluid can be by applying Foreign matter, condensation product are filtered before cloth to prevent the generation of image deflects.In addition, above-mentioned charge generation substance directly can be added individually In above-mentioned solution, it can also be added in the form of being scattered in above-mentioned charge generation layer binder resin.In addition, charge produces Generating layer can also be formed by the way that above-mentioned charge generation substance is carried out vacuum evaporation.In the form, can not also especially it use Above-mentioned charge generation layer binder resin.

The mixing of charge generation layer binder resin and charge generation substance in charge generation layer formation coating fluid Ratio is compared with 100 mass parts of charge generation layer binder resin, and charge generation substance is preferably 1~600 mass parts, more Preferably 20~600 mass parts, further preferably 50~500 mass parts.By make charge generation layer binder resin with The mixed proportion of charge generation substance is above range, excellent at following aspect：Charge generation layer formation can obtain with coating fluid High dispersion stabilization, and resistance is suppressed relatively low and can strongly inhibit with Reusability in the photoreceptor of formation Residual electric potential increase.

As charge generation layer formation with the solvent used in coating fluid, as long as using layer can be generated with dissolved charge with viscous The solvent of agent resin is tied, for example, methyl ethyl ketone, methyl isopropyl Ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, benzene can be enumerated The ketone series solvents such as ethyl ketone, tetrahydrofuran, twoThe ether series solvents such as alkane, dioxolanes, diethylene glycol dimethyl ether, methyl cellosolve, 4- Methoxyl group -4-methyl-2 pentanone, ethyl cellosolve, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, the tert-butyl alcohol, sec-butyl alcohol, The fragrance such as the ester series solvents such as the alcohol series solvents such as propyl alcohol, ethyl acetate, tert-butyl acetate, toluene, dimethylbenzene, dichloromethane, chlorobenzene Belong to a large amount of solvents such as halogen-based solvents, hexamethylene, pyridine, the diethylamides such as solvent, dichloroethanes, trichloroethanes, but do not limit In them.These solvents, which can be used alone, or to be mixed with two or more by a kind.

As electroconductive particle, the metal oxygen in the process for dispersing of charge generation substance, with interlayer formation coating fluid The process for dispersing of compound particle can similarly enumerate ultrasonic dispersing machine, ball mill, sand mill and homogeneous mixer etc., but unlimited Due to them.

In addition, as the coating method of charge generation layer formation coating fluid and the drying means of coated film, can enumerate with The identical method of the method enumerated with the drying means of coated film as the coating method of interlayer formation coating fluid.

(charge transport layer)

The charge transport layer used in the photoreceptor of the present invention preferably comprises charge conveying substance and binder resin is (following Also referred to as charge transport layer binder resin).

Charge as charge transport layer conveys substance, and the substance as delivered charge can for example enumerate triphenylamine derivative Object, hydrazone compound, compound of styryl, benzidine compound, adiene cpd etc., but it is not limited to them.Charge is defeated Substance is sent to can be used alone or two or more is applied in combination.In addition, above-mentioned charge conveying substance can also using commercially available product Use composite.As the synthetic method of charge conveying substance, such as Japanese Unexamined Patent Publication 2010-26428 publications, Japan can be enumerated The synthetic method of charge conveying substance (charge-transporting compound) recorded in special open 2010-91707 publications etc..

Charge transport layer is not particularly limited with binder resin, and well known resin can be used.As its concrete example, example Such as, polycarbonate resin, polyacrylate resin, polyester resin, polystyrene resin, styrene-acrylonitrile copolymerization can be enumerated Resin, polymethacrylate resin, styrene-methacrylate copolymer resin etc. are preferably polycarbonate resin. These charge transport layers can be used alone with binder resin or two or more be applied in combination.Comprising bisphenol-A (BPA) as single The makrolon A of body ingredient, poly- carbonic acid 1,1-bis(4-hydroxyphenyl)-cyclohexane (bisphenol Z, BPZ) as monomer component is included Ester Z, as the polycarbonate resin of monomer component and BPA and dimethyl are included comprising dimethyl bisphenol A (dimethyl BPA) The polycarbonate resins of BPA as monomer component etc. are more preferable from the perspective of resistance to anti-thread breakage, wearability, charged characteristic.

Resistance is suppressed relatively low and can strongly inhibit the residual electric potential with Reusability from photoreceptor Increase viewpoint to set out, the content ratio of the charge conveying substance in charge transport layer is compared with charge transport layer binder resin 100 mass parts are preferably 10~500 mass parts, more preferably 20~250 mass parts.

Antioxidant, electronic conductor, stabilizer, silicone oil etc. can be further added in charge transport layer.For example, for Antioxidant is preferably the antioxidant disclosed in Japanese Unexamined Patent Publication 2000-305291 publications etc., excellent for electronic conductor Elect the electronic conductor disclosed in Japanese Unexamined Patent Application 50-137543 publications, Japanese Unexamined Patent Application 58-76483 publications etc. as.

The thickness of charge transport layer according to charge convey the characteristic of substance, the characteristic of charge transport layer binder resin and Content ratio etc. and it is different, be preferably 5~40 μm, more preferably 10~30 μm.

As above the forming method of charge transport layer is not particularly limited, for example, can be formed in the following way：It is inciting somebody to action Charge conveying substance (CTM) is added in the solution that charge transport layer binder resin is formed with the dissolving of well known solvent, is used Dispersion machine makes it scattered and prepares charge transport layer formation coating fluid.The charge transport layer formation coating fluid is produced in charge The surface of generating layer is coated with (using coating machine with certain film thickness) and forms coated film, which is dried.As coating side The same method of method with being illustrated in one, above-mentioned most surface layer can be used in method.It, can as coating method and drying means With using the same method of method with being illustrated in above-mentioned superficial layer one.In addition, charge transport layer coating fluid can lead to It crosses and filters foreign matter, condensation product before coating to prevent the generation of image deflects.In addition, above-mentioned charge conveying substance can be directly single It solely makes an addition in above-mentioned solution, can also be added in the form of being scattered in above-mentioned charge transport layer binder resin.In addition, Charge transport layer can also be formed by the way that above-mentioned charge is conveyed substance progress vacuum evaporation.It, can not also be special in the form Not using above-mentioned charge transport layer binder resin.

As charge transport layer with the solvent used in coating fluid, can enumerate with charge generation layer with being used in coating fluid The identical solvent of solvent.

In addition, as the coating method of charge transport layer formation coating fluid and the drying means of coated film, can also enumerate The identical side of the method enumerated with the coating method as charge generation layer formation coating fluid and the drying means of coated film Method.

Charge in charge transport layer coating fluid conveys mixing of the substance compared with charge transport layer binder resin It compared with charge transport layer with 100 mass parts of binder resin is preferably 10~500 mass parts that ratio, which is, and further preferably 20 ~250 mass parts.By the way that charge transport layer is made with the mixed proportion that binder resin and charge convey substance to be above range, Following aspect is excellent：Charge transport layer formation can obtain high dispersion stabilization with coating fluid, and electric in the photoreceptor of formation Resistance is suppressed increase that is relatively low and can strongly inhibiting the residual electric potential with Reusability.

(charged roller (charged mechanism：Roller strap electric system))

Charged roller 11 is for making the charged mechanism of (negative) electricity of the surface band of Electrophtography photosensor, is for being shone with electronics The surface of phase photoreceptor close to (form for including contact) and apply electrified voltage close to band electrically (comprising contact) Charged mechanism (roller strap electric system).Representative embodiment party as the charged roller 11 for possessing the charged mechanism (roller strap electric system) Formula, for example, as shown in figure 3, assigning elasticity while being stacked on the surface of plug 11a and reducing band electric noise and obtaining Onto the surface of the elastic layer 11b of the uniform adaptation to photoreceptor 10, as needed be stacked for using charged roller 11 as The resistance key-course 11c of the resistance of high uniformity integrally is obtained, superficial layer 11d is stacked on resistance key-course 11c and is formed Roller become using close to the direction of photoreceptor 10 by pressing spring 11e and to the surface of photoreceptor 10 with defined pressure crimping And the composition of the state of charged clamping part is formed, it is driven in the rotation of photoreceptor 10 and rotates.

Plug 11a is formed such as the metal by iron, copper, stainless steel, al and ni or by rust-preventing characteristic in order to obtain, anti-scratch Wound property and carry out the material that forms of plating in these metallic surfaces in the range of electric conductivity is not damaged and form, outer diameter For example, 3~20mm.

Elastic layer 11b in rubber elastomeric material such as by adding the electrically conductive microparticle formed by carbon black, carbon graphite Or material obtained by conductive salt particle being made of alkali metal salt, ammonium salt etc. etc. is formed.As the concrete example of elastic material, example Such as, natural rubber, propylene diene methylene rubber (EPDM), SBR styrene butadiene rubbers (SBR), organic can be enumerated Silicon rubber, polyurethane rubber, chlorohydrin rubber, isoprene rubber (IR), butadiene rubber (BR), nitrile butadiene rubber (NBR) and the synthetic rubber such as neoprene (CR)；The resins such as polyamide, polyurethane resin, organic siliconresin and fluororesin； Or foaming bodies such as foam sponge etc..The size of elasticity can be adjusted by adding processing oil, plasticizer etc. in elastic material.

The volume resistivity of elastic layer 11b is preferably 1 × 10¹~1 × 10¹⁰The scope of Ω cm.In addition, elastic layer 11b Thickness be preferably 500~5000 μm, more preferably 500~3000 μm of scope.The volume resistivity of elastic layer 11b be according to The value that JIS K6911-2006 are measured.

Resistance key-course 11c is set as a whole with being waited for the purpose of uniform resistance by charged roller 11, also may be used Not have.Resistance key-course 11c can set or have by coating by being coated with the material with moderate conductivity The pipe of moderate conductivity is set.

As form resistance key-course 11c specific material, can enumerate polyamide, polyurethane resin, The resins such as fluororesin, organic siliconresin；Rubbers such as chlorohydrin rubber, polyurethane rubber, neoprene and acrylic rubber etc. The electrically conductive microparticle being made of carbon black, carbon graphite etc. is added in basic material；By electric conductivity titanium oxide, electroconductive zinc oxide, lead The conductive metal oxide particle of the compositions such as electrical tin oxide；Conductive salt particle be made of alkali metal salt, ammonium salt etc. etc. Material obtained by conductive agent.

The volume resistivity of resistance key-course 11c is preferably 1 × 10-²~1 × 10¹⁴The scope of Ω cm, more preferably 1 ×10¹~1 × 10¹⁰The scope of Ω cm.In addition, the thickness of resistance key-course 11c is preferably 0.5~100 μm, more preferably 1 ~50 μm, further preferably 1~20 μm of scope.The volume resistivity of resistance key-course 11c is according to JIS K6911- 2006 values measured.

Superficial layer 11d is due to preventing the surface of plasticizer in elastic layer 11b etc. to obtained charged roller 11 from oozing out Purpose, the sliding on surface for obtaining charged roller or the purpose of flatness or there are during the defects of pin hole on photoreceptor 10 Purpose of the generation of prevent leakage etc. and set, can be set by being coated with the material with moderate conductivity, Huo Zhetong Pipe of the coating with moderate conductivity is crossed to set.

When superficial layer 11d is set, as specific material, it can enumerate in polyamide, gather by coating material The resins such as urethane resin, acrylic resin, fluororesin and organic siliconresin；Chlorohydrin rubber, polyurethane rubber, neoprene and third The electrically conductive microparticle being made of carbon black, carbon graphite etc. is added in the basic materials such as alkene nitrile system rubber；By electric conductivity titanium oxide, conduction Material obtained by the conductive agents such as the conductive metal oxide particles of compositions such as property zinc oxide, conductive tin oxide.As coating Method can enumerate Dipcoat method, rolling method and spraying process etc..

In addition, by coated tube and when setting superficial layer 11d, as specific pipe, can enumerate will be in nylon 12, tetrafluoro Ethylene-perfluoroalkyl vinyl ether copolymer resins (PFA), polyvinylidene fluoride, hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) copolymer resins (FEP)；Polystyrene, polyolefin, polyvinyl chloride, polyurethane series, Polyester and the thermoplastic elastomers such as polyamide-based Material obtained by above-mentioned conductive agent is added in body etc. is shaped to the pipe of tubulose.The pipe can be the pipe of heat-shrinkable or The pipe of non-thermal contraction.

The volume resistivity of superficial layer 11d is preferably 1 × 10¹~1 × 10⁸The scope of Ω cm, more preferably 1 × 10¹~ 1×10⁵The scope of Ω cm.In addition, the thickness of superficial layer 11d is preferably 0.5~100 μm, and more preferably 1~50 μm, into one Step is preferably 1~20 μm of scope.The volume resistivity of superficial layer 11d is the value measured according to JIS K6911-2006.

In addition, the surface roughness Rz of superficial layer 11d is preferably 1~30 μm, more preferably 2~20 μm, further preferably For 5~10 μm of scope.The surface roughness Rz of superficial layer 11d is the value measured according to JIS B0601-2001.

In charged roller 11 as above, band electrical bias voltage is applied to the plug 11a of charged roller 11 by using power supply S1, Make the charged defined current potential for specified polarity in surface of photoreceptor 10.Here, band electrical bias voltage for example can be only direct current Voltage, but from charged excellent in uniformity aspect, the vibration voltage of overlapping alternating voltage preferably on DC voltage. Band electrical bias voltage can for example be set to -2.5~-1.5kV or so.

If display is formed using an example of the charged condition of charged roller 11 shown in Fig. 3 with electrical bias voltage DC voltage (Vdc) is -500V, and alternating voltage (Vac) is frequency 1000Hz, the sine wave of peak-to-peak voltage 1300V, passes through application The band electrical bias voltage, the equally charged surface of photoreceptor 10 is -500V.

The charged roller 11 is set to the length of the length of the long side direction based on photoreceptor 10, and the length of long side direction for example may be used It is set to 320mm.

In the image forming apparatus, photoreceptor 10 is driven in rotation, and the surface of the photoreceptor 10 is utilized to be applied from power supply S1 It is defined current potential that the charged roller 11 of state with electrical bias voltage is equally charged.

Next, equally charged photoreceptor 10 using exposure mechanism 12 is exposed and forms electrostatic latent image, this is quiet Electric sub-image is developed using developing mechanism 13, so as to form toner image.The toner image being formed on photoreceptor 10 utilizes Transfer means 14 are transferred on the transfer materials P conveyed according to opportunity, using separating mechanism (not shown) from photoreceptor 10 It separates and is fixed in fixing mechanism 17, so as to form visual picture.

Toner residued on photoreceptor 10 etc. is removed using the cleaning balde 18a of cleaning mechanism 18, is removed Toner etc. lodge in storage part 18b.

The image forming apparatus of the present invention is not limited to form as described above or with involved by multiple photoreceptors And the color image forming device of composition that is set along middle transfer body of image formation unit.

It is preferably more in the color image forming device for having the image formation unit involved by multiple photoreceptors in this set All photoreceptors in a photoreceptor are made of above-mentioned photoreceptor, if at least one in multiple photoreceptors is by above-mentioned photoreceptor structure Into then can obtain following effect：Using the charged mechanism close to band electrically when band is (negative) electric (during roller strap electricity) inhibit Discharge deterioration, photoreceptor can obtain high wearability, and being imaged as good image, (it is steady that the image of formation can obtain high image It is qualitative).

(toner and developer)

The toner used in the image forming apparatus of the present invention is (negative) charging property toner.The image of the present invention is formed The toner used in device can be that crushed toner can also be polymerization toner, in the image forming apparatus of the present invention In, from the perspective of the image for obtaining high image quality, it is preferable to use the polymerization toners made with polymerization.

Polymerization toner refers to the generation of the binder resin by that will form toner and the shape of toner particle shape Into with for obtain the starting monomer of binder resin polymerize and chemical treatment thereafter as needed carries out parallel and obtains The toner arrived.

More specifically, refer to obtain the process of resin particle via by polymerisations such as suspension polymerisation, emulsion polymerizations The process for making resin particle fuse with one another carried out behind as needed and the toner formed.

The volume average particle size of toner, i.e. above-mentioned 50% particle volume diameter (Dv50) is preferably 2~9 μm, and more preferably 3 ~7 μm.By being set to the scope, resolution ratio can be improved.And then it is small particle size toner by being combined with above range The amount of the toner of fine particle size can be reduced simultaneously, can improve the reproducibility of point image for a long time, and it is good to form clarity Stabilization image.

Toner according to the present invention can be used only as monocomponent toner, can also be mixed and conduct with carrier Two-component developing agent uses.

As monocomponent toner in use, non-magnetic single component developer can be enumerated or contained in toner The magnetic single component developer of 0.1~0.5 μm or so of magnetic particle, it is any all to can be used.

In addition, mixed with carrier and as two-component developing agent in use, magnetic particle as carrier, can be used The known materials such as the alloy of metals such as the metals such as iron, ferrite, magnetic iron ore, these metals and aluminium, lead.Particularly preferably Ferrite particles.It is preferably 15~100 μm as the volume average particle size of above-mentioned magnetic particle, more preferably 25~80 μm.

Toner, the measure of volume average particle size of carrier can be spread out by the representative laser for possessing wet type dispersion machine Formula particle size distribution device " HELOS " (SYMPATEC company systems) is penetrated to be measured.

Carrier is preferably that magnetic particle further makes magnetic particle point by the resin-coated carrier formed or in resin Dissipate the so-called resin dispersion type carrier formed.Resin as coating forms, and is not particularly limited, for example, alkene can be used Hydrocarbon system resin, phenylethylene resin series, styrene acrylic resin, silicon-type resin, ester system resin or fluoropolymer system tree Fat etc..In addition, as forming the resin of resin dispersion type carrier, it is not particularly limited, well known resin, example can be used Such as, styrene acrylic resin, polyester resin, fluorine resin, phenolic resin etc. can be used.

More than, embodiments of the present invention are specifically illustrated, but embodiments of the present invention are not limited to Example is stated, various changes can be applied.

Embodiment

Hereinafter, the specific embodiment of the present invention is illustrated, but the present invention is not limited to them.

(making of composite construction particle (1))

As shown in Fig. 4 (a), prepare barium sulfate (BaSO₄) particle (the average grain diameter 80nm of primary particle) is as in core The inorganic particulate 21 used.

Make the untreated inorganic particulate (BaSO₄Particle) 200g is scattered in water 3L and obtains slurry.Add in the slurry Sodium stannate (the Na that the content for adding tin is 41 mass %₂SnO₃) 208g and its dissolving is made to obtain mixed slurry.

While cycle the mixed slurry, while being irradiated using the ultrasonic vibrator for the part for being arranged at circulating path Ultrasonic wave.The frequency of ultrasonic wave is 40kHz, output power 570W.While ultrasonic wave is irradiated to the mixed slurry for cycling, on one side 20 mass % dilute sulfuric acid aqueous solutions are added in the mixed slurry and carry out in tin and.Dilute sulfuric acid aqueous solution was added with 60 minutes Until the pH for being added to mixed slurry is 2.5.After neutralization, by the aluminum chloride hexahydrate (AlCl of 0.69g₃·6H₂O) (purity 97%) mixed slurry is made an addition to, stirs the mixed slurry.The precursor (1) of target composite construction particle is obtained as a result,.

After cleaning the precursor (1) using warm water, dewatering and filtering is carried out.The filter cake of the precursor being recovered by filtration (1) is carried It is placed in horizontal pipe stove, in 2 volume %H₂/N₂Under atmosphere with 500 DEG C reduction calcine 1 it is small when.As a result, as shown in Fig. 4 (b), system Make the composite construction grain that coating is formed doped with the tin oxide (mixing Al tin oxide) 23 of aluminium on above-mentioned core (inorganic particulate) 21 (1) 25 (the average grain diameter 100nm of primary particle) of son.The average grain diameter of the primary particle of composite construction particle (1) 25 passes through base It is measured (same as below) in the volume reference particle size determination of the particle of laser diffractometry.

By composite construction particle (1) 25, the surface conditioning agent of 100 mass parts：" KBM-503 " is (as containing methyl-prop The 3- methacryloxypropyls of the silane coupling agent of enoyl-：Shin-Etsu Chemial Co., Ltd's system) 2.5 mass parts and 1000 mass parts of methyl ethyl ketone are put into wet type sand mill (the aluminium oxide pearl of diameter 0.5mm), with 30 DEG C Mix 6 it is small when.Thereafter, methyl ethyl ketone and aluminium oxide pearl are filtered out, (powder) are dried with 60 DEG C, so as to obtain as (1) 25 surface of composite construction particle is subjected to the composite construction particle that forms of surface treatment with surface conditioning agent shown in Fig. 4 (c) 〔1〕25a.As composite construction particle (1) 25a being surface-treated.In addition, above-mentioned composite construction particle (1) 25 Surface except comprising coating inorganic particulate 21 mix 23 surface of Al tin oxide in addition to, also (mix Al oxygen comprising 21 surface of inorganic particulate Change 23 coil serving of tin (shot-like particle) mutual gap etc.).By using fluorescent x-ray analyzer " XRF-1700 (Co., Ltd. islands Tianjin makes made) " it detects the peak of Si and confirms：Pass through above-mentioned surface treatment, (1) 25 (inorganic particulate of composite construction particle 21 and coating inorganic particulate 21 mix Al tin oxide 23) surface be coated (formation Surface Treated Films by above-mentioned surface conditioning agent 27)。

By mixing 97 mass parts composite construction particle (1) 25a being surface-treated and fluororesin：“Novec (registered trademark) 2702 " (3M company systems) 3 mass parts can obtain the composite junction that will be surface-treated as shown in Fig. 4 (d) Structure particle (1) 25a (inorganic particulate 21 being surface-treated and the table for mixing Al tin oxide 23 being surface-treated Face etc.) with composite construction particle (1) 25b for forming of fluororesin coating.As carried out surface treatment and fluororesin coating Composite construction particle (1) 25b.By using fluorescent x-ray analyzer " XRF-1700 (Shimadzu Scisakusho Ltd's system) " It detects the peak of fluorine element and confirms：It is coated by above-mentioned fluororesin, the composite construction particle (1) being surface-treated 25a surfaces (inorganic particulate 21 being surface-treated and the surface for mixing Al tin oxide 23 being surface-treated etc.) By the coating of above-mentioned fluororesin (forming fluororesin film 29).

The doping for being coated the Al of the tin oxide of the inorganic particulate (core) of composite construction particle (1) 25b of gained is 0.4 Mass parts, the volume resistivity for having carried out composite construction particle (1) 25b of surface treatment and fluororesin coating is 1.0 × 10⁷Ω cm.Here, the doping of Al is represented compared with the ratio (mass parts) (same as below) for mixing 100 mass parts of Al tin oxide.Al's Doping is measured (same as below) using foregoing ICP luminescence spectrometers analyzer.In addition, the measure of volume resistivity It is carried out using press-powder resistance measurement system (Mitsubishi Chemical PD-41) and determination of resistivity device (Mitsubishi Chemical MCP-T600).It will examination Sample 15g puts into probe tube, and probe unit is fixed on PD-41, is measured using MCP-T600 and is applied using hydraulic jack 500kgf/cm²Resistance value during pressure.Press-powder resistance (volume resistivity) is calculated by the resistance value and sample thickness that are measured (same as below).

(making of composite construction particle (2))

In the making of composite construction particle (1), by aluminum chloride hexahydrate (AlCl₃·6H₂O additive amount) is by 0.69g 0.35g is changed to, in addition, table has been carried out with what is used in making embodiment 2 in the same manner as the making of composite construction particle (1) Surface treatment and the composite construction particle (2) (the average grain diameter 100nm of primary particle) of fluororesin coating.

The doping for being coated the Al of the tin oxide of the inorganic particulate (core) of the composite construction particle (2) of gained is 0.2 matter Part is measured, the volume resistivity for having carried out the composite construction particle (2) of surface treatment and fluororesin coating is 1.0 × 10⁵Ωcm。

(making of composite construction particle (3))

In the making of composite construction particle (1), by aluminum chloride hexahydrate (AlCl₃·6H₂O additive amount) is by 0.69g 0.17g is changed to, in addition, table has been carried out with what is used in making embodiment 3 in the same manner as the making of composite construction particle (1) Surface treatment and the composite construction particle (3) (the average grain diameter 100nm of primary particle) of fluororesin coating.

The doping for being coated the Al of the tin oxide of the inorganic particulate (core) of the composite construction particle (3) of gained is 0.1 matter Part is measured, the volume resistivity for having carried out the composite construction particle (3) of surface treatment and fluororesin coating is 1.0 × 10⁴Ωcm。

(making of composite construction particle (4))

In the making of composite construction particle (1), the inorganic particulate used in core is changed to silica (SiO₂) Particle (the average grain diameter 80nm of primary particle) in addition, embodiment is made in the same manner as the making with composite construction particle (1) The progress used in 4 surface treatment and composite construction particle (4) (average grain diameter of primary particle of fluororesin coating 100nm)。

The doping for being coated the Al of the tin oxide of the inorganic particulate (core) of the composite construction particle (4) of gained is 0.4 matter Part is measured, the volume resistivity for having carried out the composite construction particle (4) of surface treatment and fluororesin coating is 1.0 × 10⁶Ωcm。

(making of composite construction particle (5))

In the making of composite construction particle (1), the inorganic particulate used in core is changed to silica (SiO₂) Particle (the average grain diameter 30nm of primary particle) in addition, embodiment is made in the same manner as the making with composite construction particle (1) The progress used in 5 surface treatment and the composite construction particle (5) (the average grain diameter 50nm of primary particle) of fluororesin coating.

The doping for being coated the Al of the tin oxide of the inorganic particulate (core) of the composite construction particle (5) of gained is 0.4 matter Part is measured, the volume resistivity for having carried out the composite construction particle (5) of surface treatment and fluororesin coating is 1.0 × 10⁷Ωcm。

(making of composite construction particle (6))

In the making of composite construction particle (1), the inorganic particulate used in core is changed to silica (SiO₂) Particle (the average grain diameter 80nm of primary particle), by aluminum chloride hexahydrate (AlCl₃·6H₂O additive amount) is changed by 0.69g For 0.35g, in addition, carried out with what is used in making embodiment 6 in the same manner as the making of composite construction particle (1) at surface Reason and the composite construction particle (6) (the average grain diameter 100nm of primary particle) of fluororesin coating.

The doping for being coated the Al of the tin oxide of the inorganic particulate (core) of the composite construction particle (6) of gained is 0.2 matter Part is measured, the volume resistivity for having carried out the composite construction particle (6) of surface treatment and fluororesin coating is 1.0 × 10⁵Ωcm。

(making of composite construction particle (7))

In the making of composite construction particle (1), the inorganic particulate used in core is changed to silica (SiO₂) Particle (the average grain diameter 30nm of primary particle), by aluminum chloride hexahydrate (AlCl₃·6H₂O additive amount) is changed by 0.69g For 0.35g, in addition, carried out with what is used in making embodiment 7 in the same manner as the making of composite construction particle (1) at surface Reason and the composite construction particle (7) (the average grain diameter 50nm of primary particle) of fluororesin coating.

The doping for being coated the Al of the tin oxide of the inorganic particulate (core) of the composite construction particle (7) of gained is 0.2 matter Part is measured, the volume resistivity for having carried out the composite construction particle (7) of surface treatment and fluororesin coating is 1.0 × 10⁵Ωcm。

(making of composite construction particle (8) and (9))

In the making of composite construction particle (1), by aluminum chloride hexahydrate (AlCl₃·6H₂O additive amount) is by 0.69g 0.52g is changed to, in addition, is made in the same manner as the making with composite construction particle (1) and has carried out surface treatment and fluororesin The composite construction particle (the average grain diameter 100nm of primary particle) of coating.Here, answering the gained used in embodiment 8 The composite construction particle (8) that structured particles are set to carry out surface treatment and fluororesin coating is closed, by what is used in embodiment 9 The composite construction particle of gained is set to carry out the composite construction particle (9) of surface treatment and fluororesin coating.

The inorganic particulate (core) of composite construction particle (8) and (9) (identical composite construction particle) obtained by being coated The doping of the Al of tin oxide be 0.3 mass parts, carried out surface treatment and fluororesin coating composite construction particle (8) and (9) volume resistivity of (identical composite construction particle) is 1.0 × 10⁶Ωcm。

(making of composite construction particle (10))

In the making of composite construction particle (1), the inorganic particulate used in core is changed to aluminium oxide (Al₂O₃) grain Sub (the average grain diameter 80nm of primary particle), in addition, embodiment 10 is made in the same manner as the making with composite construction particle (1) The middle progress used surface treatment and composite construction particle (10) (average grain diameter of primary particle of fluororesin coating 100nm)。

The doping for being coated the Al of the tin oxide of the inorganic particulate (core) of the composite construction particle (10) of gained is 0.4 matter Part is measured, the volume resistivity for having carried out the composite construction particle (10) of surface treatment and fluororesin coating is 1.0 × 10⁷Ωcm。

(making of composite construction particle (11))

In the making of composite construction particle (1), without utilizing surface conditioning agent：" KBM-503 " is (as containing methyl The 3- methacryloxypropyls of the silane coupling agent of acryloyl group：Shin-Etsu Chemial Co., Ltd System) surface treatment, carry out fluororesin coating and make in embodiment 11 and use in the same manner as the making with composite construction particle (1) Carried out fluororesin coating composite construction particle (11) (the average grain diameter 100nm of primary particle).

The doping for being coated the Al of the tin oxide of the inorganic particulate (core) of the composite construction particle (11) of gained is 0.4 matter Part is measured, the volume resistivity for having carried out the composite construction particle (11) of fluororesin coating is 1.0 × 10⁷Ωcm。

(making of composite construction particle (12))

In the making of composite construction particle (1), fluororesin is not mixed：" Novec (registered trademark) 2702 " (3M companies System) (being coated without fluororesin), with making the progress used in embodiment 12 in the same manner as the making of composite construction particle (1) The composite construction particle (12) (the average grain diameter 100nm of primary particle) of surface treatment.

The doping for being coated the Al of the tin oxide of the inorganic particulate (core) of the composite construction particle (12) of gained is 0.4 matter Part is measured, the volume resistivity for the composite construction particle (12) being surface-treated is 1.0 × 10⁷Ωcm。

(making of composite construction particle (13))

In the making of composite construction particle (1), inorganic particulate is changed to antimony doped tin oxide (Mitsubishi General Materials electronics It is melted into the ATO transparent conductivity powder T-1 series of Co. Ltd. system) (the average grain diameter of primary particle：20nm), it is not inorganic to this Particle is doped coating treatment and the surface treatment of the tin oxide of Al, in the same manner as the making with composite construction particle (1) into Row fluororesin is coated and makes the inorganic particulate (the average grain diameter 20nm of primary particle) for having carried out fluororesin coating.

The inorganic particulate that this has been carried out to fluorine processing has carried out what fluororesin was coated directly as what is used in comparative example 1 (not being nucleocapsid) composite construction particle (13) (the average grain diameter 20nm of primary particle) uses.

The inorganic particulate of (not being nucleocapsid) composite construction particle (13) of gained with doped with Al due to not adulterated Tin oxide carry out coating treatment, therefore the doping of Al cannot be measured.In addition, carried out fluororesin coating (is not nucleocapsid Structure) composite construction particle (13) volume resistivity be 1.0 × 10⁴Ωcm。

(making of composite construction particle (14))

In the making of composite construction particle (1), the inorganic particulate used in core is changed to barium sulfate (BaSO₄) grain Sub (the average grain diameter 10nm of primary particle), in addition, comparison example 2 in the same manner as the making with composite construction particle (1) The middle progress used surface treatment and the composite construction particle (14) (the average grain diameter 30nm of primary particle) of fluororesin coating.

The doping for being coated the Al of the tin oxide of the inorganic particulate (core) of the composite construction particle (14) of gained is 0.4 matter Part is measured, the volume resistivity for having carried out the composite construction particle (14) of surface treatment and fluororesin coating is 1.0 × 10⁷Ωcm。

(making of composite construction particle (15))

In the making of composite construction particle (1), the inorganic particulate used in core is changed to barium sulfate (BaSO₄) grain Sub (the average grain diameter 280nm of primary particle), in addition, comparison example 3 in the same manner as the making with composite construction particle (1) The middle progress used surface treatment and composite construction particle (15) (average grain diameter of primary particle of fluororesin coating 300nm)。

The doping for being coated the Al of the tin oxide of the inorganic particulate (core) of the composite construction particle (15) of gained is 0.4 matter Part is measured, the volume resistivity for having carried out the composite construction particle (15) of surface treatment and fluororesin coating is 1.0 × 10⁷Ωcm。

(making of composite construction particle (16))

In the making of composite construction particle (1), substitute aluminum chloride hexahydrate (AlCl₃·6H₂O) 0.69g and be changed to Tantalic chloride (TaCl₅) 1.03g, in addition, used in the same manner as the making of composite construction particle (1) in comparison example 4 The composite construction particle (16) (the average grain diameter 100nm of primary particle) of surface treatment and fluororesin coating is carried out.

The doping for being coated the Ta of the tin oxide of the inorganic particulate (core) of the composite construction particle (16) of gained is 0.4 matter Part is measured, the volume resistivity for having carried out the composite construction particle (16) of surface treatment and fluororesin coating is 1.0 × 10⁶Ωcm。

(making of composite construction particle (17))

In the making of composite construction particle (1), inorganic particulate is changed to ultrafine barium sulfate particle (Sakai chemical industry strain formula BARIFINE (registered trademark) series of commercial firm) (the average grain diameter of primary particle：100nm), without the oxidation doped with Al Tin carries out coating treatment, carries out surface treatment and fluorine processing in the same manner as the making of composite construction particle (1) to the inorganic particulate And make the inorganic particulate (the average grain diameter 100nm of primary particle) for having carried out surface treatment and fluororesin coating.

The inorganic particulate that this has been carried out to surface treatment and fluorine processing has carried out surface directly as what is used in comparative example 5 (not being nucleocapsid) the composite construction particle (17) (the average grain diameter 100nm of primary particle) of processing and fluororesin coating makes With.

The inorganic particulate of the composite construction particle (17) of gained is not due to to be carried out doped with the tin oxide of Al at coating Reason, therefore the doping of Al cannot be measured.In addition, (not being nucleocapsid) that has carried out surface treatment and fluororesin coating is compound The volume resistivity of structured particles (17) is 1.0 × 10²Ωcm。

(embodiment 1)

(making of photoreceptor (1))

(1) making of conductive support body

Machining is carried out to the surface of the aluminium support body (outer diameter 30mm, length 360mm) of drum type, makes surface roughness The conductive support body (1) of Rz=1.5 (μm).

(2) formation in interlayer

Using sand mill as dispersion machine, by batch-type to following raw materials carry out 10 it is small when disperse, preparation interlayer It is formed with coating fluid (1).

Binder resin：Polyamide " X1010 " (Daicel Degussa company systems)

1 mass parts

Solvent：20 mass parts of ethyl alcohol

Metal oxide microparticle：Titanium oxide microparticle " SMT500SAS " (the Tayca plants of formulas of equal 0.035 μm of the primary particle size of number Commercial firm's system) 1.1 mass parts

The interlayer formation is coated with coating fluid (1) and shape by Dipcoat method in above-mentioned conductive support body (1) It is into coated film, the coated film is 20 minutes dry at 110 DEG C, form the interlayer (1) of 2 μm of thickness.

(3) formation of charge generation layer

Using sand mill as dispersion machine, disperse when small to following raw materials progress 10, prepare charge generation layer and form use Coating fluid (1).

The charge generation layer formation is coated on above-mentioned interlayer (1) by Dipcoat method (dip coating method) to be coated with Liquid (1) and form coated film, formed 0.3 μm of thickness charge generation layer (1).

(4) formation of charge transport layer

Following raw materials are mixed and dissolved, prepare charge transport layer formation coating fluid (1).

The charge transport layer is coated with by Dipcoat method (dip coating method) on above-mentioned charge generation layer (1) and forms use Coating fluid (1) and form coated film, the coated film is 70 minutes dry at 120 DEG C, form the charge transport layer of 20 μm of thickness 〔1〕。

(5) formation of most surface layer

By (1) 100 mass parts of composite construction particle obtained in the making of composite construction particle (1), multifunctional free radical Polymerizable compound：100 mass parts of trimethylol-propane trimethacrylate (Sartomer Company system), solvent：2- butanol 400 mass parts, solvent：40 mass parts of THF (tetrahydrofuran) mix under shading, and it is small to disperse 5 using sand mill as dispersion machine Shi Hou adds in polymerization initiator：Irgacure819 (BASF Japan company systems) 10 mass parts, being stirred under shading makes its molten Solution prepares most surface layer and is formed with coating fluid (1).

The most surface layer formation is coated on charge transport layer with coating fluid (1) using circular slip hopper apparatus (1) film is formed on, using metal halide light irradiation ultraviolet light 1 minute, forms the most surface layer of 3.0 μm of dry film thickness (1), photoreceptor (1) is completed.

(embodiment 2~12 and comparative example 1~5)

(making of photoreceptor (2)~(17))

In the formation (process) of most surface layer in the making of photoreceptor (1), by the system of above-mentioned composite construction particle (1) The composite construction particle (1) obtained in work is changed to making~composite construction particle (17) of above-mentioned composite construction particle (2) Composite construction particle (2)~(17) obtained in making, and then, being changed to the formula of table 1, (number of composite construction particle (makes Dosage)), in addition, photoreceptor (2)~(17) are made in the same manner as the making with photoreceptor (1).

The composition of photoreceptor (1)~(17) made in embodiment 2~12 and comparative example 1~5 is shown in table 1 below.

(evaluation)

(1) wearability

Using the bizhub (registered trademark) 554 of Konica Minolta Opto Inc., in 23 DEG C of room temperature, humidity 50%RH Under the conditions of, it takes pictures 30000 in Bk (black toner) position, is damaged according to the film thickness of the most surface layer for front and rear photoreceptor of taking pictures Consumption is evaluated according to following evaluation criteria.By photoreceptor (1)~(17) evaluation result is shown in table 1.

Specifically, the film thickness of the most surface layer of photoreceptor is randomly to measure homogeneous film thickness part at 10 (to make film thickness Graph changes part to exclude the film thickness of the front end of coating and rear end portion), it is averaged film thickness of the value as most surface layer. Determining film thickness device uses the determining film thickness device " EDDY560C " (HELMUT FISCHER GMBTE CO company systems) of vortex-like fashion, The difference of the film thickness of most surface layer before and after calculating long duration test (taking pictures 30000) is as film thickness waste (μm).As durable Experiment under the conditions of 23 DEG C of room temperature, humidity 50%RH, is implemented the character image that image rate is 5% is horizontal with A4 in Bk positions Into mode carry out the experiments of 30000 single side continuous printings (taking pictures).

- evaluation criteria of wearability (film thickness waste)-

◎：Film thickness waste is less than 0.3 μm of abrasion (very excellent)

○：Film thickness waste is for 0.3 μm less than 0.6 μm of abrasion (excellent)

△：Film thickness waste is for 0.6 μm less than 1 μm of abrasion (having no problem in practical)

×：Film thickness waste is 1 μm or more of abrasion (problematic in practical)

(2) electrical characteristics

Using Konica Minolta Opto Inc. bizhub (registered trademark) 368 in 23 DEG C of room temperature, humidity 50%RH items Under part by initial stage potential setting be 600 ± 30V, measurement exposure after surface potential, evaluated according to following evaluation criteria.It will Photoreceptor (1)~(17) evaluation result is shown in table 1.

- evaluation criteria of electrical characteristics (surface potential after exposure)-

◎：Surface potential after exposure is less than 60V (very excellent)

○：Surface potential after exposure is 60V less than 90V (excellent)

△：Surface potential after exposure (has no problem) in practical for 90V less than 120V

×：Surface potential after exposure is more than 120V (problematic in practical)

(3) filament characteristic

Using bizhub (registered trademark) C368 of Konica Minolta Opto Inc. in 30 DEG C of room temperature, humidity 80%RH In 1 black line (1 point) of Bk (black toner) position output, (judgement schematics is 1 point of clathrate under the conditions of (high humidity environment) Judgement schematics.Evaluate the horizontal line of the grid), formed black line is observed with light microscope, is carried out according to following evaluation criteria Evaluation.By photoreceptor (1)~(17) evaluation result is shown in table 1.

- evaluation criteria of filament characteristic (the optical microphotograph sem observation of black line)-

◎：Black line does not interruptedly form (very excellent) zero with certain line width：The line width of black line is a part of disorderly Disorderly but without interrupting (excellent)

△：Part has the position (having no problem in practical) that black line interrupts

×：Black line (problematic in practical) is not formed

According to table 1 as a result, the most surface layer of photoreceptor contains composite construction particle and resinoid bond, above-mentioned composite junction The core of structure particle is coated tin oxide, above-mentioned composite construction doped with aluminium (Al) for inorganic particulate and on above-mentioned inorganic particulate The average grain diameter of the primary particle of particle is photoreceptor (1)~(12) of the embodiment 1~12 of 50~200nm in each assessment item In obtain good evaluation.

On the other hand, composite construction particle and resinoid bond, above-mentioned composite construction are contained in the most surface layer of photoreceptor The core of particle is coated tin oxide, above-mentioned composite construction grain doped with aluminium (Al) for inorganic particulate and on above-mentioned inorganic particulate The average grain diameter of the primary particle of son is any one of important document of 50~200nm without the photoreceptor of the comparative example 1~5 met (13) in~(17), there are problems by 1 or more in wearability, electrical characteristics and filament characteristic.

Claims

1. a kind of Electrophtography photosensor is sequentially laminated with charge generation layer, charge transport layer in conductive support body, special Sign is,

The layer for forming the most surface of the Electrophtography photosensor contains core for inorganic particulate and the quilt on the inorganic particulate The composite construction particle formed doped with the tin oxide of aluminium is covered,

The average grain diameter of the primary particle of the composite construction particle is 50~200nm.

2. Electrophtography photosensor according to claim 1, which is characterized in that the inorganic particulate is BaSO₄、SiO₂、 Al₂O₃Any one of.

3. Electrophtography photosensor according to claim 1 or 2, which is characterized in that be coated the doping of the inorganic particulate There is the tin oxide of aluminium compared with the scope that the doping of the Al of 100 mass parts of tin oxide is 0.05~1 mass parts, the composite junction The volume resistivity of structure particle is 10¹~10⁸Ωcm。

4. Electrophtography photosensor described in any one of claim 1 to 3, which is characterized in that the composite construction grain Son using compared with 100 mass parts of composite construction particle not being surface-treated as having in the range of 0.5~10 mass parts The surface conditioning agent of polymerism reactive group be surface-treated,

The surface conditioning agent is the silane coupling agent containing acryloyl group or methylacryloyl.

5. Electrophtography photosensor according to any one of claims 1 to 4, which is characterized in that the composite construction grain Son compared with 100 mass parts of composite construction particle as the fluororesin in the range of 1~10 mass parts to be coated.

6. according to Electrophtography photosensor according to any one of claims 1 to 5, which is characterized in that form the electronics and shine The layer of the most surface of phase photoreceptor further contains resinoid bond,

The content of the composite construction particle is compared with the scope that 100 mass parts of resinoid bond are 50~250 mass parts.

7. Electrophtography photosensor according to claim 6, which is characterized in that the resinoid bond is polymerism chemical combination The polymerizing curable object of object.

8. a kind of image forming apparatus, which is characterized in that have：

Electrophtography photosensor according to any one of claims 1 to 7,

For make the surface of the Electrophtography photosensor charged charged mechanism,

Formed for the surface irradiation light to the charged Electrophtography photosensor electrostatic latent image exposure mechanism,

The development of toner image is formed for supplying toner to the Electrophtography photosensor for being formed with electrostatic latent image Mechanism and

For the toner image on the surface of the Electrophtography photosensor to be transferred to the transfer means of recording medium,

The charged mechanism be apply for being approached with the surface of the Electrophtography photosensor electrified voltage close to charged The charged mechanism of mode.